title 不飽和カルボニル化合物への共役付加を基盤とする選択 ......1...

Title 不飽和カルボニル化合物への共役付加を基盤とする選択的反応の開発( Dissertation_全文 )

Author(s) 百武龍一

Citation 京都大学

Issue Date 2016-03-23

URL httpsdoiorg1014989doctork19661

Right 許諾条件により本文は2017-03-22に公開許諾条件により要旨は2016-06-22に公開

Type Thesis or Dissertation

Textversion ETD

Kyoto University

不飽和カルボニル化合物への共役付加を基盤とする

選択的反応の開発

2015

百武龍一

1

不飽和カルボニル化合物への共役付加を基盤とする選択的反応の開発

目次

理論の部

第一章序論 5

第二章競合する β-脱離反応を抑制した不斉記憶型分子内共役付加反応による

多置換 β-ラクタムの不斉合成 6

第一節先行研究及び著者の研究方針 6

第二節環化前駆体の合成 8

第三節反応条件の最適化 8

第四節基質の検討 11

第五節平衡反応による反応挙動の考察 12

第六節絶対配置の決定及び反応メカニズムの考察 12

第三章不斉炭素に隣接した C-N 軸性不斉エノラートを経由する β-ラクタム形成の

立体化学 16

第一節過去の関連研究と著者の研究方針 16


第三節トレオニン誘導体を用いた環化条件の検討と生成物の絶対配置の決定 18

第四節立体化学経路の解明 20

第四章 αβγδ-不飽和環状ケトンを用いた位置選択的 aza-Morita-Baylis-Hillman 反応の開発 23


第二節最適条件の検討 24

第三節基質の検討 25

第四節メカニズム解析 26

第五章結論 33

実験の部

第二章に関する実験 38

第三章に関する実験 49

第四章に関する実験 56

2

引用文献一覧 68

謝辞 73

3

理論の部

4

5

第一章緒言

有機合成化学は生理活性物質や機能性材料医薬品化学製品等の供給法を確立することで

医学薬学材料化学等の幅広い学問領域及び産業分野に貢献してきたそれら多様な有機化合

物群の基本骨格は炭素であるため炭素-炭素結合形成反応の開発は本学問領域の最重要課題の一

つである本課題は官能基変換を足がかりに多くの方法が開発されてきたその中でも αβ-不飽

和カルボニル化合物への炭素求核剤を用いた共役付加反応は1887 年 Michael らにより安定化カ

ルボアニオンと αβ-不飽和カルボニル化合物との反応が系統的に研究されて以降1 カルボニル β

位に新たな炭素-炭素結合を導入する基盤的な炭素骨格構築法として知られている2 特に β位に

置換基を有する αβ-不飽和カルボニル化合物とエノラートとの反応では連続する多置換炭素骨格

を形成するため不斉反応を含め多数の報告が存在する3 また求核剤の共役付加により生成

するエノラートを次なる反応の求核種として活用する多段階反応も報告されている4さらに第

三級アミンやホスフィンのようなルイス塩基を求核触媒として αβ-不飽和カルボニル化合物への

共役付加に用いた場合生じたエノラートは種々のアルデヒドやイミンと α位で炭素-炭素結合を

形成し続く触媒の脱離により対応するアリルアルコールやアリルアミンを与える (Baylis-

Hillman 反応)5 このように共役付加反応は用いる求核剤や反応条件の選択により様々な形式

の炭素-炭素形成反応への展開が可能であるしかしながら多官能基性化合物や高歪み化合物

の合成法へと展開する場合その反応様式の多様さが競合する副反応として問題となる6 このよ

うな背景のもと著者は共役付加を基盤とし多数の反応経路が存在しうる反応において目的の

反応のみを選択的に進行させることで未解決の分子変換を実現し有機合成化学の最重要課題の

一つである炭素-炭素結合形成反応の多様性を広げるべく以下の研究を行った

(1) 競合する β-脱離反応を抑制した不斉記憶型分子内共役付加反応による多置換 β-ラクタムの不

斉合成

(2) 不斉炭素に隣接した C-N 軸性不斉エノラートを経由する β-ラクタム形成の立体化学

(3) αβγδ-不飽和環状ケトンを用いた位置選択的 aza-Morita-Baylis-Hillman 反応の開発

6

第二章競合する β-脱離反応を抑制した

不斉記憶型分子内共役付加反応による多置換 β-ラクタムの不斉合成

第一節先行研究及び著者の研究方針

共役付加反応は原子効率が 100 の炭素-炭素結合形成反応であり連続する多置換炭素骨格の

構築法として古くから用いられてきた信頼性の高い反応である著者の所属する研究室では外部

不斉源を必要としない不斉記憶型反応の特徴を活かした不斉共役付加反応の開発に取り組んでき

た7 不斉記憶とは不斉炭素上での脱プロトン化によって一見消失する不斉情報が動的なキラ

リティーとして中間体に転写される現象でありこれを利用した不斉反応が可能である8その一

例としてアミノ酸誘導体から生成する C-N 軸性不斉エノラートを用いた分子内共役付加反応に

よる連続三置換-四置換炭素を有する含窒素複素環の高立体選択的合成法がある (Scheme 2-1 eq

1)7a 本反応は五ndash七員環形成には適するが四員環に代表される高歪み化合物の合成においては

エノラートの共役付加体の環歪みと共役付加反応の可逆性のため目的物は得られていなかっ

た (eq 2)

Scheme 2-1 不斉記憶型分子内共役付加反応の scope and limitation

このような状況下所属研究室でエノラートを経由する不斉記憶型共役付加反応による多置換

β-ラクタム合成法が開発された (Scheme 2-2)9 本反応では Cs2CO3 EtOH 系を用いる事が重要で

ある即ち弱塩基 Cs2CO3 (共役酸の pKa~10) を用いることで 1 (エステル -位の pKa~23) か

ら極低濃度のキラルエノラート A が生成するため Michael 受容体を持つエノラート同士の分

子間反応に由来する副反応が抑制され分子内反応のみが選択的に進行し-ラクタムエノラー

ト B が生成するエノラート B は四員環の環歪みおよび環状置換基の立体反発により高度

に歪んだ骨格を有していると予想される実際このエノラート構造のDFT計算によるとC(3)-C(4)

結合は 163 Aringとなり極度に伸張している事が示唆された即ち B はその不安定性のため容

易に A への逆反応が進行すると考えられるがB は少量でも生成すると溶媒の EtOH から迅速

なプロトン化を受けるためβ-ラクタム 2 を高収率高エナンチオ選択的に与えたこのように

本法はエノラート中間体を経る反応にも関わらずプロトン源で反応が促進される点も興味深い

7

このプロトン化による反応促進においてエノラート A はプロトン化を受けず (プロトン化を受

けるとラセミ化を起こすため高光学純度の生成物が期待できない)9 -ラクタムエノラート B の

みがプロトン化を受ける点も肝要であり巧みに制御されているこれはプロトン化を受ける

炭素の立体環境に起因すると考えられるまたC-N 軸性不斉エノラート A は C-N 軸の回転に

よりラセミ化が進行するためその速度よりも速く分子内環化する事で生成物に不斉が誘導され

るこのように本反応では分子間反応逆共役付加反応C-N 軸性不斉エノラートのプロトン

化によるラセミ化及び C-N 軸の回転によるエノラートのラセミ化の四つの副反応が競合する中

巧みにその選択性が制御され目的の分子内環化が優先して進行しキラル β-ラクタムを与える

Scheme 2-2 基質 1 を用いた分子内不斉記憶型共役付加反応による β-ラクタムの不斉合成

本研究ではβ位に脱離しうる置換基を有するアミノ酸誘導体 (セリンシステイントレオニ

ン) を出発物として用いさらに競合する副反応である β-脱離反応を抑制した不斉記憶型 β-ラク

タム合成に取り組んだカルボニル β 位にアルコキシ基 (OR) 基などの脱離基を持つ基質の α-

アルキル化に際しては基質を環状化合物にする等の工夫が必要であるが10 著者はそれとは異

なるアプローチにより β-脱離反応の抑制を試みた即ちC-N 軸性不斉エノラートの分子内共役

付加反応と β-脱離反応が競合する事から環化速度を向上させる事で相対的に β-脱離の速度を下

げる方策をとった11

本基質を用いた際に得られる β-ラクタムは四置換炭素含有アミノ酸骨格を有しており特に α

α-二置換セリン骨格は免疫抑制物質 ISP-I12 やプロテアソーム阻害剤 lactacystin

13 などの生理活性

物質に見られる構造であるため抗菌剤としての潜在的意義のみならず医薬品や全合成の中間体

としての適用も期待されるβ-ラクタムは抗菌作用コレステロール吸収阻害作用 14セリンプ

ロテアーゼ阻害作用 15抗癌作用 16等の魅力的な生物活性を示すのみならずペプチドミメティ

ック 17や β-アミノ酸等価体キラルビルディングブロック 18として利用されておりそれら合成

法の開発が活発に行われているその合成法は

多岐に渡るが大部分はイミンとケテンを用い

る[2+2]環化付加反応を基本としたものであるた

めその新規合成法の開発は有用である19

8

第二節環化前駆体の合成

市販の N-Boc-L-serine(OBn)-OH (3) の TFA 処理による脱 Boc 化後SOCl2EtOH 条件によるエ

チルエステル化PMB-Cl を用いた N-PMB 化酸クロリドを用いた N-アシル化により環化前

駆体 4 へと導いた (Scheme 2-3)

Scheme 2-3 セリン誘導体 4 の合成

第三節反応条件の最適化

まず過去の不斉記憶型反応を参考に塩基の検討を行った (Table 2-1)7 強塩基である LDA や

KOH を用いた場合には目的の環化体は全く得られず複雑な混合物を与えるのみであった

(entries 1 and 2)これは強塩基によるエノラートの高濃度生成により分子内反応に優先して分子間

反応が進行したためと考えられるフェニルアラニン誘導体を用いた際の最適条件 (Cs2CO3

EtOH) では所望の環化体 5 が 62 収率で得られたもののベンジルオキシ基がエトキシ基に

変換された環化体 6 も 34 収率で得られた (entry 3)本副生成物 6 は 4 の-脱離体 7 に対し

系中のエタノールが塩基性条件下エキソオレフィンにマイケル付加した後環化反応が進行し

得られた化合物と考えられる (scheme 2-4)副生成物 6 の生成抑制を目指し側鎖水酸基の保護

基の検討を行った (entries 4-6)側鎖水酸基が無保護の基質を EtOH 中Cs2CO3 で処理したとこ

ろ複雑な混合物を与えた (entry 4)側鎖水酸基をメトキシメチル (MOM) 基t-ブチルジフェ

ニルシリル (TBDPS) 基で保護した基質を同様に処理すると副生成物 6 が主生成物として得ら

れた (entries 5 and 6)6 の光学純度は 0 ee であった (entry 7)

Table 2-1 セリン誘導体 4 を用いた β-ラクタム合成の初期検討

9

Scheme 2-4 本反応の推定メカニズム

そこで塩基を Cs2CO3 に固定し本反応の中間体であるエノラート C のラセミ化半減期や β-

脱離反応速度エノラートの反応性に影響を与えると考えられる溶媒温度の検討を行った (Table

2-2)溶媒に EtOH CH3CN toluene DMF 等を用い種々検討を行ったが収率光学純度と

もに満足のいく結果ではなかった (entries 1-6)一方でt-amyl alcohol を用いた場合 5 が 92 収

率と良好に得られたが光学純度は中程度であった (entry 7)

Table 2-2 セリン誘導体 4 を用いた反応検討

この原因は環化速度が β-脱離反応やキラルエノラートのラセミ化の速度に対し充分でないこ

と並びに環化体のエノラート D から C-N 軸性不斉エノラート C への速い逆反応の進行が考

えられた (Scheme 2-4)そこでエノラート D の安定化による環化速度の向上を目的にマイケ

ル受容体部位としてビニリデンマロネート構造を持つセリン誘導体 8 を合成し反応条件を精

査した (Table 2-3)先の最適条件であった t-amyl alcohol を溶媒に用いた場合反応は極めて遅く

所望の環化体 9 はほとんど得られなかった (Table 2-3 entry 1)これはt-amyl alcohol (pKa~17 in

10

H2O) では環化体のエノラート E (pKa~12 in H2O) のプロトン化が困難なことに起因していると

考えたそこでE の効率的なプロトン化を目的に酸性度の高いプロトン化剤として phenol

(pKa~10 in H2O) を添加した (Table 3 entry 2)その結果反応速度は著しく上昇し20 min の反

応時間で 9 が 98収率で得られたしかしながら光学純度はそれぞれ 69 ee 62 ee と依然

中程度であったそこで光学純度の向上を目的として反応温度を 0 ordmC に下げたところ所望

の環化体 9 の光学純度はそれぞれ 79 ee 69 ee と向上した (entry 3)溶媒を CH3CN に変更

しより低温下で検討を行ったところ (t-amyl alcohol の融点 -9 oC)温度を下げるほど光学純度

は向上した (entries 4-6)これは反応温度の低下により C-N 軸性不斉エノラートのラセミ化半

減期が延長したためと考えられるしかし環化速度も減少し反応完結には時間を要した

Table 2-3 セリン誘導体 8 を用いた反応条件の最適化

そこで反応速度に影響を与えると考えられるプロトン化剤の検討を行った (Table 2-4)溶媒

を CH3CN 反応温度を 0 ordmC反応時間を 1 時間に固定し種々のプロトン化剤を検討したそ

の結果pKa = 84 の 2-bromophenol (enrty 1) や pKa = 125 の trifluoroethanol (entry 7) を用いた時に

は原料が残存したがpKa = 93~87 のプロトン化剤を用いた時には反応が完結した (entries 2-5)

entry 1 と entry 7 の結果から適切な酸性度のプロトン化剤を選択することで反応速度が改善さ

れる事が分かったこれはプロトン化剤の酸性度が高いと塩基 Cs2CO3 との酸塩基反応が進行

し系内の塩基やプロトン源の濃度が下がることまたプロトン源の酸性度が低いと環化体のエ

ノラート E の効率的なプロトン化が起こりにくいことが原因と考えられるまた

hexafluoro-2-propanol を用いた時に光学純度が最も高くなった (entry 5)そのため以降では本化

合物を最適なプロトン化剤としてさらに検討を行ったその結果反応温度が -10 ordmC の時に収

率 98dr = 6733光学純度 92 ee90 ee で目的の環化体が得られ本条件を最適条件とし

た (entry 6)以上の結果はマイケル受容体部位を αβ-不飽和ジエステル構造としたことで環化速度

が向上しかつ環化体のエノラートがプロトン源により迅速にプロトン化された事で逆反応が抑制され

たためと考えられる

11

Table 2-4 プロトン化剤の検討

第四節側鎖水酸基の保護基並びに基質一般性の検討

基質一般性を調べる目的でβ位の置換基の検討を行った (Table 2-5 entries 1-3)水酸基がMOM

基TBDPS 基で保護されたセリン誘導体 10 12 を用いた場合にも β-脱離反応を起こすことなく

所望の環化体が 90 以上の収率で得られTBDPS 用いた時に光学純度はこれまでで最高の 96

ee であった(entries 2 and 3)本結果から水酸基保護基が嵩高いほど光学純度が高くなる傾向が

見られたまたβ 位に硫黄原子を有するシステイン誘導体 14 を用いた場合でも所望の環化体

が 90 収率dr=5050光学純度がともに 91 ee で得られた一般的にチオールはアルコー

ルに比べ共役酸の酸性度が大きいため β-脱離反応が進行しやすいと考えられるが本反応におい

て β-脱離体は全く検出されなかった

Table 2-5 基質一般性の検討

12

第五節平衡反応による反応挙動の考察

フェニルアラニン誘導体を用いた不斉 β-ラクタム合成と同様本反応には逆反応が存在すると

考えられたそこでその存在の実験的証明を試みたすなわち環化体のジアステレオマー 9a 9b

をそれぞれ単離し環化反応条件に付した (Scheme 2-5)その結果単一の 9a 9b を用いたにも

関わらず生成物はジアステレオマー混合物となったフェニルアラニン誘導体 1 を用いる反応

で (Scheme 2-2) EtOH の変わりに EtOD を用いても β-ラクタム 2a 2b の C(3) 位は全く重水

素化されずC(1rsquo) 位が重水素化された知見を考慮すると生成物がジアステレオマー混合物とな

るのは β-ラクタム環上の水素の脱プロトン化を経て進行しているのではなく逆分子内共役付加

反応を経て進行していると考えられるまた両ジアステレオマーの光学純度の低下及び β-脱

離体は確認されなかったこのことから本反応は逆分子内共役付加による開環反応により生成

するエノラートがラセミ化や β-脱離反応を起こすことなく再び環化反応が進行することが分かっ

た

Scheme 2-5 平衡実験

第六節絶対配置及び相対配置の決定

不斉記憶型分子内共役付加反応で新たに生じた四置換炭素の絶対配置を決定するためX 線結

晶構造解析を行った (Scheme 2-6)すなわちジアステレオマー混合物の β-ラクタム 9 のエチル

エステルの脱炭酸を伴う加水分解により生成するジカルボン酸体と p-ヨードアニリンとの縮合反

応を行い分離により重原子であるヨウ素を含むマイナージアステレオマー 16 を得たその後

CH2Cl2 n-hexane から再結晶することで 98 ee の 16 を得た (Scheme 2-6)

Scheme 2-6 絶対配置決定に伴う 9 の誘導化

13

その X 線結晶構造解析の結果四置換炭素の絶対配置は R であった (Figure 2-1)このことか

ら本反応はアミノ酸由来の不斉炭素の立体反転を伴って進行することが明らかとなったこれ

は従来の不斉記憶型反応の想定されるメカニズムと一致するものである

Figure 2-1 誘導体 16 の単結晶 X 線結晶構造解析 (Probability Level = 50)

また環化体 9a 9b の相対立体配置を NOESY 測定により決定した (Figure 2-2)その結果

9a では C(3) 位メチンプロトンと C(5) 位メチレンプロトン間に相関が観測され9b では C(1rsquo)

位メチンプロトンと C(5) 位メチレンプロトン間に相関が観測されたこれらの事からC(3) 位

の置換基と C(4) 位のエトキシカルボニル基は9a は trans9b は cis の関係にある事が明らか

となった

Figure 2-2 環化体 9a 9b の相対配置絶対配置の決定

第七節反応メカニズムの考察

以上の結果から本反応の推定メカニズムを Scheme 2-7 に示したセリン誘導体の α 位の脱

プロトン化は従来の不斉記憶の知見より C 又は D のコンホメーションから進行すると考えら

れる20 先のX線結晶構造解析より本反応は不斉中心の立体反転を伴って進行していた事から

セリン α位の炭素-水素結合とN-アシル結合がアンチペリプラナーの関係にある D のコンホメー

ションのときに優先して脱プロトン化が進行しC-N 軸性不斉エノラート E が生成すると考えら

れるこの時 C-N 軸不斉は aS の立体配置を持つためC-N 軸が回転するよりも速くアミド

側にある Michael 受容体と反応すれば立体反転を伴って反応は進行するしかしながらエノ

ラート E からは (a) 分子内共役付加反応(b) β-脱離反応(c) C-N 軸の回転によるラセミ化(d)

分子間反応が起こりうる経路 (d) は弱塩基を用いるエノラートの低濃度生成により抑制した

さらに反応性の高いマイケル受容体を用い経路 (a) の反応速度を大きくする事で経路(b) (c)

は相対的に遅くなり抑制されたまたpKa=10 程度のプロトン源を添加する事で環化体のエノラ

14

ート F から G への変換が促進されたことで反応は速やかに進行したと推測される

Scheme 2-7 不斉 β-ラクタム合成の推定メカニズム

第七節計算化学を用いた β-ラクタム合成の考察

本反応条件では平衡反応であるが原料回収はなく生成物のみが得られるこのことから環歪

みがあるにも関わらず環化前駆体よりも β-ラクタムの方がエネルギー的に安定と考えられるそ

の要因解明を目的に原料と生成物のエネルギー差を両化合物の単純化した構造の DFT 計算に

より調べた Figure 2-2 MOPAC 2002 [1] Version 253 CAChe Version 75085 and the Gaussian 03

packages (Revision D 01 [2a] and Revision E 01 [2b]その結果生成物の trans 体 18 は 53

kcalmol cis 体 19 は 76 kcalmol 環化前駆体 17 より安定であることが分かった環歪みの存

在にも関わらず環化体の方が安定な理由としては開裂するアルケンがカルボニル基に挟まれて

いるため不安定でありC (sp2)-C(sp2) 結合が切れて C(sp3)-C(sp3) 結合が生成する方が有利な

ためと考えられる

Figure 2-2 DFT 計算による化合物 17-19 の相対的安定の算出

15

16

第三章不斉炭素に隣接した C-N 軸性不斉エノラートを経由する β-ラクタム形成の立体化学

第一節過去の関連研究と著者の研究方針

不斉記憶型反応は基質の中心不斉が中間体エノラートの C-N 軸不斉に転写される事で生成物の

四置換炭素が不斉構築される一方エステル β 位に中心不斉を有する基質から生成するエノラ

ートを経由する α-アルキル化反応は反応点に隣接する不斉中心の影響により生成物のエステル

α位には中心不斉が発現する (Scheme 3-1)21

Scheme 3-1 β位に中心不斉を有するエステルのジアステレオ選択的 α-アルキル化反応

そのような背景のもと著者の所属する研究室では側鎖に中心不斉を有する L-イソロイシン

L-allo-イソロイシン誘導体を用いた不斉記憶型分子間アルキル化反応において新たに構築され

る四置換炭素の不斉誘導は側鎖中心不斉の影響ではなくアミノ酸 α 位の不斉の影響が主に働く

事を明らかにしている (Scheme 3-2)22

Scheme 3-2 ジアステレオ選択的不斉記憶型反応

そこで筆者は第二章で記述した分子内共役付加反応による β-ラクタム合成法においてエステ

ル β 位に中心不斉を有する基質を用いて不斉記憶型反応を行った場合新たに構築される四置換

炭素の中心不斉は C-N 軸不斉と側鎖の中心不斉どちらに依存して構築されるのかに興味を持ち

実験的に確かめることとした (Scheme 3-2)

17

Scheme 3-2 中心不斉 vs C-N 軸不斉

その手法としてエステル α 位の絶対配置は同じ S で側鎖中心不斉が逆の絶対配置を持つジア

ステレオマーの関係にあるトレオニン誘導体allo-トレオニン誘導体を用いた β-ラクタム合成を

行うこととした (Scheme 3-3)すなわち不斉記憶型反応で四置換炭素の立体構築が制御される

場合両基質のエステル α位の不斉は S で同じであるため生成するエノラートの C-N 軸不斉も

同じ絶対配置を有しその結果両反応で得られる主生成物の四置換炭素の絶対配置は同じとなる

それに対しβ 位の中心不斉により四置換炭素の立体が構築される場合それぞれの基質の β 位

の不斉は逆の関係にあるためそれぞれの反応で得られる主生成物の四置換炭素の絶対配置は逆

になるはずである以上の理由から主ジアステレオマーの四置換炭素の絶対配置を比較するこ

とで本反応の立体化学経路が明らかにできると考え検証を行った

Scheme 3-3 不斉記憶型分子内共役付加反応による β-ラクタム合成における立体化学経路

18


市販の N-Boc-L-threonine(OBn)-OEt の TFA 処理による脱 Boc 化後N-PMB 化N-アシル化によ

り環化前駆体 20 へと導いた (Scheme 3-4)

Scheme 3-4 L-トレオニン誘導体 20 の合成

第三節トレオニン誘導体を用いた環化条件の検討と生成物の絶対配置の決定

L-トレオニン誘導体 20 をセリン誘導体を用いた β-ラクタム合成における最適条件に付した

(Table 3-1 entry 1)その結果ジアステレオマー混合物 21a 21b 21c が 77 収率21a21b21c =

741312 の比で得られたそれぞれの化合物の絶対および相対立体配置は後述する X 線結

晶構造解析および NOESY スペクトル解析により決定した次に反応時間を 24 時間に延長

したその結果二種類のジアステレオマー 21a 21b が 78 収率21a21b=8812 の比で得ら

れた (entry 2)本結果から21c は反応時間を延長した事により retro-Michael 反応を経て 21a へ

と異性化したと考えられ速度論的生成物と示唆された

Table 3-1 L-トレオニン誘導体 20 を用いた β-ラクタム合成

21a の絶対配置は誘導体 25 の X 線結晶構造解析により決定した (Scheme 3-4)21a の β-エ

トキシカルボニルエステル活性メチンのスルフェニル化によりスルフィド 22 を得た後m-CPBA

によるスルフィドへの酸化加熱による syn-脱離を経て 23 を得たその後水酸化リチウムに

19

よるエステルの加水分解によりトリカルボン酸 24 とした後二塩化オキサリルDMF を用いた

酸クロリドへと変換続く p-ヨードアニリンとの縮合により重元素であるヨウ素を含む 25 を

得たその後CH2Cl2toluene n-hexane から再結晶する事で単結晶を得たその X 線結晶構造解

析より四置換炭素の絶対配置は R であった (Figure 3-1)

Scheme 3-4 環化体 15a の四置換炭素の絶対配置の決定

Figure 3-1 誘導体 25 の X 線結晶構造解析 (Probability Level = 30)

また21c の絶対配置は 21c の固体を CH2Cl2n-hexane から再結晶する事で単結晶を作成しそ

の X 線結晶構造解析により求めたその結果四置換炭素の絶対配置は R であった

20

Figure 3-2 環化体 21c の X 線結晶構造解析 (Probability Level = 50)


どちらの化合物でも C(3) 位メチンプロトンと C(5) 位メチンプロトン及びC(6) 位メチルプロト

ン間に相関が観測されたこれらの事からC(3) 位の置換基と C(4) 位のエトキシカルボニル基

は cis の関係にある事が明らかとなった21a の C(4) 位の絶対配置は X 線結晶構造解析より R

であった事から21b の四置換炭素の絶対配置は 21a と逆の S と分かった


以上の事からL-トレオニン誘導体を用いた β-ラクタム合成で得られる主生成物の新たに構築さ

れた四置換炭素の絶対立体配置は R と分かった

第四節立体化学経路の解明

次に L-トレオニン誘導体 20 とは β位の不斉が逆の関係にある L-allo-トレオニン誘導体 26

を β-ラクタム合成の最適条件に付した所 (反応時間 24 h) ent-21b と ent-21a が dr=973 83

収率で得られた (Scheme 3-5)ent-21b は 21b の鏡像異性体であることからその四置換炭素の

絶対配置は逆の関係にあり R と分かったすなわち両反応で得られるメジャージアステレオ

マー 21a ent-21b の四置換炭素の絶対配置は同じ R であったことから本反応は中心不斉の影

響を凌駕して C-N 軸不斉により四置換炭素の立体化学が決定されている事が分かった

L-トレオニン誘導体 20 を用いた場合に比べL-allo-トレオニン誘導体 26 を用いた場合の方が

ジアステレオマー比が高かった事から20 より生成するエノラート (aS R) は mismatched

21

chirality で26 より生成するエノラート (aS S) は matched chirality であると考えられるこれ

は側鎖の OBn 基とエノラートが同一平面上にある active conformer から反応が進行すると考え

た場合(aS R) のエノラートはメチル基とマイケルアクセプターとの立体障害があるのに対し

(aS S) のエノラートでは水素原子とマイケルアクセプターの立体反発が小さいために L-allo-ト

レオニン誘導体を用いた場合の方がジアステレオ選択性が高かったと考察した23

Scheme 3-5 L-allo-トレオニン誘導体 26 を用いた β-ラクタム合成と立体化学経路の決定

22

23

第四章 αβγδ-不飽和環状ケトンを用いた

位置選択的 aza-Morita-Baylis-Hillman 反応の開発


aza-MBH 反応は第三級アミンやホスフィンといった Lewis 塩基存在下αβ-不飽和カルボニル

化合物がカルボニル α位でイミンと炭素-炭素結合を形成し対応するアリルアミンを与える有用

な炭素骨格構築反応である24 そのメカニズムは求核触媒の共役カルボニル化合物への付加

(scheme 4-1 step 1)生じたエノラートのイミンへの求核攻撃 (step 2)アミドアニオンの分子内水

素引き抜きによる触媒の脱離 (step 3) であり3 つのステップの反応が連続的に進行する事で他

の方法では困難な分子変換が実現できる

Scheme 4-1 aza-Morita-Baylis-Hillman 反応

生成物はカルボニル基オレフィン保護アミノ基を有する多官能基性化合物であるがさら

なる多官能基性化合物を得る目的で電子求引基を有する共役ジエン I を用いた報告もある

(Scheme 4-2)それらジエンの電子求引基としてはスルホン25a アシル25bエステル25cニト

リル 25d 等が用いられているまた続く環化反応により二環性化合物 25e やジヒドロピリジン環

25f を与える報告例もある本反応ではα-付加体 K と γ-付加体 L が得られうるはずだが通常

α-付加体 K のみが得られ共役ジエンを用いた γ-選択的 aza-MBH 反応の報告は皆無である26

27 これはγ-付加体 L の選択的形成には求核触媒のジエン I の δ位への位置選択的共役付加

並びに生じたジエノラート J2 の γ位における位置選択的炭素-炭素結合形成という二つの位置

選択性を制御する困難さに起因すると考えられるこのような背景のもとaza-MBH 反応の新展

開を目指し触媒制御による位置選択的 aza-MBH 反応の開発に着手した本法で得られる

aza-MBH 付加体 K L は三つの求電子部位に加え求核部位である保護アミノ基を有する多官能

基性化合物であり生理活性物質や天然物合成の際のビルディングブロックとして活用し得る

24

Scheme 4-2 αβγδ-不飽和カルボニル化合物 I を用いた aza-MBH 反応

二つの理由から基質として 3-vinylcyclopent-2-en-1-one 27 を選択したひとつは得られる化

合物の有用性の観点からであるシクロペンタン骨格は天然物や生理活性物質等に幅広く見られ

る骨格でありそれら合成中間体としての利用が期待される27 もうひとつの理由は求核触媒

の δ 位選択的共役付加を優先させるためである通常電子求引基を有する共役ジエンは 16-付

加反応に優先して 14-付加反応が進行する事が知られているが29 30 27 は β位が二置換であるた

め立体的要因で 14-付加が進行しにくく無置換の δ位での付加が進行しやすいと考えられる30

その後のジエノラート J2 のイミンへの付加の位置選択性はジエノラート J2 の性質のチュー

ニングにより達成することとしたすなわちジエノラートの反応部位はその構造と生成条件に

依存して決まると考えられ32 用いる求核触媒によって生成するジエノラート J2 の反応性を制

御可能と考え以下検討を行った

第二節最適条件の検討

上記研究方策に則りMeOH 溶媒中ジエン 27 とイミン 28a を種々の求核触媒 (DBU PBu3

DABCO DMAP) 1 等量で処理した (Table 1 entries 1-4)その結果PBu3 DBU を用いた際には複

雑な混合物を与えた (entries 1 2) DABCO を用いた際には目的の α-付加体 29a が 92 収率で

得られた (entry 3)一方 DMAP を用いた際には 23 収率と低収率ながら γ-付加体 30a が選

択的に得られたそこでα-付加体を得る最適な触媒を DABCO γ-付加体を得る最適な触媒を

DMAP とし溶媒のスクリーニングを行った (entries 5-11)DABCO を用いた場合極性溶媒を

用いた際に反応が円滑に進行する傾向が見られ溶媒に関係なく α-付加体のみが選択的に得られ

た (entries 5-7)検討の結果 α-付加体 29 を得る条件としてDABCOMeOH 条件を最適とし

た (entry 3)次に DMAP を用い溶媒検討を行った (entries 8-11)CH3CN CHCl3 DMF THF を用

いて検討を行った所DABCO の場合とは異なり溶媒により収率位置選択性に影響が見られ

非極性溶媒を用いた際に良好な結果を与えた即ちCHCl3 中 27 と 28a を 1 当量の DMAP で

処理するとaza-MBH 付加体が 91収率29a30a=1387 の比で γ-付加体が優先的に得られ本

条件を γ-付加体を得る最適条件とした (entry 9)またDABCO DMAP を触媒量 (20 mol) 用い

25

た場合でも選択性に大きな影響を与えず所望の付加体が得られた (entries 12 13)

Table 4-1 ジエン 27 を用いた位置選択的 aza-MBH 反応の検討

第三節基質一般性の検討

導き出した最適条件下ジエン 27 と種々のイミン 28 の aza-MBH 反応を行った (Table 2)イ

ミン 28 の芳香環の電子状態置換基の位置によらずDABCO を用いた場合にはα-付加体 29 の

みが 41-68 収率で得られDMAP を用いた場合にはγ-付加体 30 が 27ndash89 収率87ndash96 の

位置選択性で得られたイミンの MeOH に対する溶解性が悪い場合はDMF や CH3CN

CHCl3MeOH 溶媒を用いて反応を行ったまたアリール基上に電子求引性の置換基を持つイミ

ンほど反応が早く進行する傾向が見られた

26


第四節メカニズム解析

ジエン 27 に対して触媒が付加する位置を調べるため重水素化実験を行った (Scheme 4-4) 27

を重メタノール中塩基で処理した結果DABCO DMAP どちらを用いた際にも γ位の D 化が α

位の D 化に優先して進行したこのことから27 の α 位 γ 位の D 化はDMAP DABCO が

27 の δ位へ付加することで生成するジエノラートを経由して進行した事が示唆されたまた27

の αrsquo位の D 化は塩基による脱プロトン化を経て進行したと考えられる

Scheme 4-4 重水素化実験

27

次に位置選択性発現のメカニズムを探るためα-付加体 29aγ-付加体 30a を DMAP 条件及

び DABCO 条件に付した (Scheme 4-5)その結果いずれの反応でも出発原料のみが回収された

この結果から生成物間に平衡はなく29a と 30a は速度論的生成物である事が分かった


さらに本反応の律速段階に関する知見を得るためHammett プロットを行った (Scheme 4-6)

求核触媒として DABCO を用いた aza-MBH 反応において p-位に置換基を有する芳香族 N-トシ

ルアルジミンの無置換の芳香族N-トシルアルジミンに対する相対速度を競争実験によって求めた

その相対速度 krel を生成物の比と変換率から算出したところそれぞれ 346 (p-CF3 置換体)046

(p-Me 置換体)033 (p-OMe 置換体) であったHammett プロットを行うと log10 (kXkH) 値は σ

値 (置換基定数) と高い相関を示しρ = 126 (r2 = 098) であった33 34 ρ 値が正の値を示した事

から律速段階の遷移状態では反応中心に負電荷が生じていると考えられ本値は Mannich 反応

の段階の値を反映していると考察した

Scheme 4-6 Hammett プロット

28

次にDABCO を用いた系における重水素同位体効果を調べた (Scheme 4-7)27 および α-d-27

を基質としDABCO を触媒とした aza-MBH 反応の反応速度論解析を行ったその結果27 と

α-d-27 とで反応速度差は見られずkHkD=1 と算出されたこの結果で算出された kHkD 値から

一次同位体効果はないと考えられ本反応の律速段階に Scheme 4-1 の step 3 に示すような α位

水素引き抜きを伴う触媒の脱離は関与していない事が分かった

Scheme 4-7 DABCO を用いた条件における重水素同位体効果

さらにDMAP を用いた系における重水素同位体効果を調べた (Scheme 4-8)27 および

ααrsquoγ-d3-27 を基質としDMAP を触媒とした aza-MBH 反応の反応速度論解析を行ったその

結果27 を基質とした場合の生成物への変換の反応速度定数 kH は 00416 h-1ααrsquoγ-d3-27 を基

質とした場合の生成物への変換の反応速度定数 kH は 00103 h-1 と算出された

Scheme 4-8 DMAP を用いた条件における重水素同位体効果

29

また27 および ααrsquoγ-d3-27 を用いた aza-MBH 反応における α-付加体と γ-付加体の生成比

を調べた (Figure 4-1)その結果27 を用いた aza-MBH 反応における生成物の比はα-付加体

29a γ-付加体 30a = 22 78 であり γ-付加体が α-付加体の生成に優先したのに対しααrsquoγ-d3-27 を

用いた場合α-付加体 αrsquoγ-d2-29a γ-付加体 ααrsquo-d2-30a = 58 42 となりα-付加体が γ-付加体の生

成に優先した

Figure 4-1 Scheme 4-8 の実験における各反応時間の生成物中の γ-付加体の割合

先の反応速度定数と生成物の割合からα-付加体へと変換される際の反応速度定数比

kHαkDα と γ-付加体へと変換される際の反応速度定数比 kHγkDγを算出した (Scheme 4-9)そ

の結果kHαkDα = 153kHγkDγ = 75 と算出されたこの結果で算出された kHkD 値からγ-

30

付加体への経路においては一次同位効果が観測されたと考えられるすわなちγ-付加体への経

路における律速段階は触媒の脱離の段階である事が分かった

Scheme 4-9 重水素同位体効果の評価

以上の結果から想定される本反応の推定メカニズムを Scheme 4-10 に示したまず触媒は 27

の δ位に求核攻撃しジエノラート δ-DABCO 又は δ-DMAP が生成するこれはDMAP 条件

での γ-付加体の生成及び Scheme 4-4 に示した重水素化実験から支持されるDABCO を用いた系

における律速段階はScheme 4-6 の Hammett-Plot の結果 (ρ=126)及び Scheme 4-7 において重

水素同位体効果が見られなかった事からstep 2 の Mannich 反応の段階である事が示唆された

これらの事からDABCO を用いた際に α-付加体が選択的に得られるメカニズムは二つ考えられ

る一つはジエノラート δ-DABCO が α位で選択的にイミンへの求核攻撃を起こし中間体 α-M

が生成した後触媒の脱離が円滑に進行することで α-付加体 29 を与えるメカニズムである (path

a)もう一つはジエノラート δ-DABCO は γ位においてもイミンと反応し中間体 γ-M を与え

るもののstep 3 の触媒の脱離により γ-付加体 30 が生成する反応の障壁が高くretro-Mannich 反

応が優先し最終的に α-付加体 29 を与える Curtin-Hamett 型の反応メカニズムである (path b)

中間体 α-M からの触媒の脱離が速い要因としてはアミドアニオンに引き抜かれるプロトンが

エステル α位かつアリル位のため酸性度が大きい事に起因すると考察した35 DMAP を用いた系

における γ-付加体を与える経路の律速段階はScheme 4-8 及び Scheme 4-9 より一次同位体効果

が観測された事から step 3 の触媒の脱離でありDABCO を用いた場合とは律速段階が異なる事

31

が分かった以上の結果から想定される γ-付加体が選択的に得られるメカニズムはDABCO を

用いた場合と同様二つ考えられる一つはδ-DMAP から α-N に優先して γ-N が生成すること

で γ-付加体が高選択的に得られるメカニズムであり (path c)もう一つは α-Nγ-N が同程度

あるいは α-N が優先して生成するもののα-N から α-付加体を与える経路の障壁が γ-N から γ-

付加体を与える経路の障壁よりも高く最終的に γ-付加体が選択的に得られる Curtin-Hamett 型の

反応メカニズムである (path d)この場合 DABCO を用いた反応では α-M の α位プロトンの

酸性度が γ-M の γ-位プロトンより高いのに対しDMAP を用いた反応では逆に γ-N の γ位プロ

トンの酸性度が α-N の α位プロトンより高いという前提が必要となるこの一つの可能性として

はσC-N+

(DMAP) と γ-N の γ位プロトンとの軌道相互作用が考えられるしかしながら現段階

では中間体 α-N γ-N の生成比や触媒の脱離過程の活性化エネルギーに関する知見が得られて

いないため今後は DFT 計算を用いた解析等の検討が必要である

以上のことからaza-MBH 反応における位置選択性はそれぞれのジエノラート δ-DABCO

δ-DMAP の反応性の違いあるいは触媒の脱離能の差に起因して発現している事が示唆された

Scheme 4-10 位置選択的 aza-MBH 反応の推定メカニズム

以上のメカニズム解析よりDMAP を用いた aza-MBH 反応において律速段階は step 3 の触媒

の脱離反応であったことから本段階が促進されれば αγ-選択性に影響が見られると考えた触

媒の脱離はプロトン源の添加により促進されるという知見から36 プロトン源の検証をした

(Table 4-3)その結果フェノールを添加した際に γ-位選択性の向上が見られた

32

Table 4-3 プロトン源の位置選択性に及ぼす影響

33

第五章結論

著者は共役付加を基盤とし多数の反応経路が存在する反応において目的の反応のみを選択的

に進行させることで未解決の分子変換を実現し有機合成化学の最重要課題の一つである炭素-炭

素結合形成反応の多様性を広げるべく以下の三つの研究を行った即ち競合する β-脱離反応

を抑制した共役付加反応による高歪み β-ラクタムの不斉合成法の開発その立体化学経路の解明

ならびに位置選択的 aza-MBH 反応を開発した以下に本研究の成果を要約する

1 競合するβ-脱離反応を抑制した不斉記憶型分子内共役付加反応による多置換β-ラクタムの不斉

合成

当研究室で開発した α-アミノ酸誘導体を用いた不斉記憶型分子内共役付加反応による多置換 β-

ラクタムの不斉合成法をβ 位に脱離しうる置換基を有するセリン酸誘導体及びシステイン誘

導体に適用可能な方法として開発したいずれの基質を用いた反応でも β-脱離体は検出されなか

った本反応はフェニルアラニン誘導体を用いた時と同様立体反転を伴って四置換炭素が構築

される事を明らかにした本反応では分子間反応β-脱離反応C-N 軸の回転によるエノラート

のラセミ化逆共役付加反応の四つの副反応が競合する中目的の分子内環化が優先して進行し

多置換 β-ラクタムを高収率高エナンチオ選択的に与えた分子間反応は弱塩基を用いた C-N 軸

斉不斉エノラートの低濃度生成により抑制したβ-脱離反応は従来は基質を環状化合物にする

等の工夫が必要であったが著者は電子吸引性の高いマイケルアクセプターを用いる事で分子内

環化速度を大きくすることで本課題を克服した環化速度の向上はエノラートのラセミ化を相対

的に遅くする点でも効果的であったその際pKa=10 程度のプロトン源を添加する事により反応

速度の向上が見られたこれは環化体のエノラートをプロトン化することで生成物への変換が

促進されたためと考えられるこれにより副反応である逆共役付加反応を克服し可逆過程を有

するエノラートの共役付加反応を用いても高度に歪んだ β-ラクタム骨格構築が可能である事を示

したこのようにエノラートを中間体とする反応においてプロトン源はエノラートを失活させ

るため禁忌であったがプロトン源がエノラート反応の促進と平衡系の制御に効果的に作用する

事を明らかにした

2 不斉炭素に隣接した C-N 軸性不斉エノラートを経由する β-ラクタム形成の立体化学

カルボニル β 位に中心不斉を有するアミノ酸誘導体を用いた不斉記憶型分子内共役付加反応に

よる多置換 β-ラクタム合成において新たに構築される四置換炭素の不斉誘導は側鎖中心不斉の

影響ではなく C-N 軸不斉の影響が主に働く事を明らかとしたその手法はエステル α 位の中

心不斉は同じ S を有し側鎖中心不斉が逆の絶対配置を持つジアステレオマーの関係にあるトレ

34

オニン誘導体L-allo-トレオニン誘導体を用いた β-ラクタム合成を行う事で確かめた即ちそ

れぞれの反応で得られる主生成物の四置換炭素の絶対配置が同じ R であることを X 線結晶構

造解析及び NOESY スペクトル解析により明らかにしC-N 軸不斉により四置換炭素構築の立

体化学が決定されたと結論付けた本結果は不斉記憶型反応において側鎖に中心不斉を有する

基質を用いた場合でも構築される四置換炭素の立体化学が予測可能であることを示している

3 αβγδ-不飽和環状ケトンを用いた位置選択的 aza-Morita-Baylis-Hillman 反応の開発

3-vinylcyclopent-2-en-1-one と様々な置換基を有する N-トシルイミンを用いた位置選択的

aza-MBH 反応を開発したα-付加体は DABCO を用いる事で完全な位置選択性でγ-付加体は

DMAP 存在下 87ndash96 の位置選択性で得られた重水素化実験よりα-付加体及び γ-付加体は求

核触媒が基質ジエンの δ 位に付加したジエノラート中間体を経由して生成する事が示唆された

また Hammett-Plot 及び重水素同位体効果実験よりDABCO を用いた場合の律速段階は炭素-

炭素結合形成DMAP を用いた系における律速段階は触媒の脱離である事が示されたまた位

置選択性は速度論支配で発現しており求核触媒とジエンより生成するジエノラートの反応性の

違い又は触媒の脱離能の差に起因する事が示唆された本知見はジエノラートの位置選択性を

触媒制御により達成する点で新しいコンセプトを提供するものであるまた用いる求核触媒に

より反応の律速段階が変化する点も興味深い

35

実験の部

36

37

General 1H NMR were measured in CDCl3 or benzene-d6 solution and referenced from TMS (000 ppm)

using JEOL ECX-400 (400 MHz) or JEOL AL-400 (400 MHz) spectrophotometers unless otherwise noted

13C NMR were measured in CDCl3 C6D6 solution and referenced to CDCl3 (770 ppm) C6D6 (1280 ppm)

using JEOL ECX-400 (100 MHz) spectrophotometer unless otherwise noted Chemical shifts are reported

in ppm IR spectra were recorded on JASCO FTIR-4200 spectrometer Mass spectra were obtained on

JEOL JMS-700 Elemental analyses were performed with CHN J-science-lab Microcoder JM10 Optical

rotations were determined on HORIBA SEPA-200 Flash column chromatography was performed on Silica

Gel (SiliaFlashreg F60 or 60N (KANTO)) Thin layer chromatography (TLC) was performed on precoated

plates (025 mm silica gel Merck Kieselgel 60F245) and compounds were visualized with UV light

followed by p-anisaldehyde stain or phosphomolybdic acid stain Preparative thin layer chromatography

(PTLC) was performed on precoated plates (05 mm silica gel Merck Kieselgel 60F245) and visualized

with UV light Anhydrous CHCl3 purchased form Kanto Kagaku was distilled over CaH2 and kept with

MS4Aring Anhydrous DMSO purchased from Wako Chemical was distilled over CaH2 and kept with MS4Aring

Anhydrous CDCl3 was distilled over CaH2 and kept with MS4Aring Anhydrous DMSO-d6 was distilled over

CaH2 and kept with MS4Aring

38

2 Experimental Procedures

21 Chapter 2

Synthesis of 4

To a solution of O-benzyl-L-serine ethyl ester hydrochloride S1 (67 g 256 mmol) in DMF (51 mL) were

added i-Pr2NEt (127 mL 768 mmol) and p-methoxybenzyl chloride (349 mL 256 mmol) successively at

rt and the resulting mixture was stirred for 24 h at 50 ˚C The reaction was quenched by addition of water

and extracted with AcOEt The extracts were washed with water dried over Na2SO4 filtered and

concentrated The residual oil was purified through open silica gel column chromatography (MeOHCHCl3

= 199) to give S2 (65 g 73) as a colorless oil To a solution of the carboxylic acid (078 g 45 mmol) in

CH2Cl2 (24 mL) were added oxalyl chloride (12 mL 113 mmol) and DMF (35 L 045 mmol)

successively at rt After being stirred for 40 min the reaction mixture was concentrated to give a crude S3

which was dissolved in CH2Cl2 (31 mL) and the resulting mixture was added to a solution of S2 (13 g 38

mmol) and i-Pr2NEt (16 mL 94 mmol) in CH2Cl2 (6 mL) at rt After being stirred for 30 min at the same

temperature the reaction was quenched by addition of sat NaHCO3 aq and extracted with CHCl3 The

extracts were washed with brine dried over MgSO4 filtered and concentrated The residual brown oil was

purified through silica gel column chromatography (Et2On-hexane = 11) to give 4 (096 g 51) as a pale

yellow oil

A 89 11 mixture of rotamers of 4 colorless oil 1H-NMR (400 MHz CHCl3) 737ndash716(m 8H)685(dd

J 68 Hz 178H) 678ndash674 (m 111H) 668 (d 156 Hz 011H) 482 (d 17 Hz 089H) 476ndash473 (m

022H) 469ndash464 (m 178H) 448ndash427 (m 233H) 420ndash388 (m 377H) 383ndash366 (m 322H) 149 (s

099H) 146 (s 801H) 123 (t 73 Hz 267H) 116 (t 73 Hz 033H) 13

C-NMR (100 MHz CDCl3)

16847 16833 16697 16579 16451 15895 15860 13758 13719 13415 13398 13273 13256

12927 12903 12847 12820 (2 peaks) 12802 12765 12751 12744 12737 11388 11343 8136

7304 6827 6689 6168 6116 6021 5918 5510 5156 2780 1395 1376 MS (FAB) mz 498

(M+H)+ 520 (M+Na)

+ 121 (base peak) HRMS (FAB) mz calcd for C28H36NO7 4982492 (M+H)

+ found

4982491

Preparation of carboxylic acis S4

39

To an ice-water-cold solution of diethyl oxomalonate (35 g 20 mmol) in benzene (40 mL) was added the

wittig reagent (75 g 20 mmol) over 5 min The resulting mixture was stirred at rt for 1 h The benzene was

removed in vacuo and Et2O was added The precipitated triphenylphosphine oxide was removed by

filtration The filtrate was concentrated and purified by silica gel column chromatography (AcOEtn-hexane

= 17) to give the desired αβ-unsaturated t-butyl ester (51 g 94) To a solution of t-butylester (51 g

186 mmol) in CH2Cl2 (13 mL) was added trifluoroacetic acid (13 mL) at 0 oC After being stirred for 15 h

the reaction mixture was concentrated in vacuo to give the crude product of S4 (46 g quant) Carboxylic

acid S5 was used in the next acid chloride formation without further purification

S4 Colorless oil 1H-NMR (400 MHz CDCl3) 689 (1H s) 437 (2H q J =73 Hz) 432 (2H q J = 69 H)

136ndash131 (6H m)

Typical procedure for synthesis of precursor of β-lactams

To a solution of carboxylic acid S4 (12 eq) in CH2Cl2 (02 M) were added oxalyl chloride (30 eq) and

DMF (catalytic amont) successively at rt After being stirred for 40 min the reaction mixture was

concentrated to give a crude acid chloride S6 which was dissolved in CH2Cl2 (02 M) and the resulting

mixture was added to a solution of L-serine derivatives S5 (10 eq) and i-Pr2NEt (30 eq) in CH2Cl2 (02

M) at 0 oC After being stirred for 30 min at the same temperature the reaction was quenched by addition

of sat NaHCO3 aq and extracted with CHCl3 The extracts were washed with brine dried over Na2SO4

filtered and concentrated The residual brown oil was purified through silica gel column chromatography to

give precursors of β-lactams

colorless oil []D18

= -16 (c 1057 CHCl3) 1H-NMR (400 MHz CDCl3) 734ndash722(m 7H)684(dd J

87 Hz 2H)451(q J 92 Hz 2H)419(q J 89 Hz 2H)383(d J = 128Hz 1H)378(s3H)

371 (dd J 50 Hz 92 Hz 1H) 364 (d J 128 Hz 1H) 363 (dd J 50 92 Hz 1H) 347 (t J =46

Hz 1H) 216 (s 1H) 125 (t 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17308 15864 13786 13173

12947 12827 12756 12750 11368 7310 7106 6080 6031 5518 5133 1422 IR (neat) cmndash1

2934 2906 2864 1736 1611 1513 1458 1368 1300 1248 1185 1102 1034 MS (FAB) mz 344

(M+H) +

366 (M+Na) +

121 (base peak) HRMS (FAB) mz calcd for C20H26NO4 (M+H) +

3441862 found

3441860

40

colorless oil 1H-NMR (400 MHz CDCl3) 766ndash762(m 4H)744ndash734(m 6H)723(dd J 87 Hz

2H) 684(d J 87 Hz 2H)425-411(m 2H) 392(dd J Hz 1H)385(dd J Hz

1H) 382 (d J 128 Hz 1H) 379 (s 3H)364 (d J 128 Hz 1H) 339 (t J 50 Hz 1H) 127 (t 69

Hz 3H) 102 (s 9H) 13

C-NMR (100 MHz CDCl3) 17339 15859 13555 13552 13308 13189

12998 12933 12764 11368 6517 6193 6071 5520 5115 2666 1919 1425 IR (neat) cmndash1

MS

(FAB) mz 492 (M+H) +

121 (base peak) HRMS (FAB) mz calcd for C29H38NO4Si (M+H) +

4922570 found

4922570

A 83 17 mixture of rotamers of 8 74 yield colorless oil []D19

= -52 (c 1087 CHCl3) 1H-NMR (400 MHz

CDCl3) 745 (s 17100 H) 735ndash717 (m 783100 H) 685 (d J = 87 Hz 166100 H) 678 (d J = 87 Hz

34100H) 477 (d J = 170 Hz 1 H) 467 (dd J = 690 37 Hz 83100 H) 465 (d J = 170 Hz 83100 H) 460

(dd J = 78 46 Hz 17100 H) 447 (d J = 156 Hz 17100 H) 439 (s 2 H) 436ndash421 (m 4H) 417-407 (m

2H) 397 (dd J = 101 74 Hz 83100 H) 392 (dd J = 101 41 Hz 83100 H) 380 (s 166100 H) 377 (s

34100 H) 377 (m 17100 H) 366 (dd J = 101 78 Hz 17100 H) 133ndash122 (m 849100 H) 118 (t J = 73

Hz 51100 H) 13

C-NMR (100 MHz CDCl3) 1684 1649 1644 1628 1591 1377 1358 1334 1292

1285 1284 1283 1282 1278 1276 1275 1140 1135 732 685 621 618 613 586 552 519 140

1391 1388 IR (neat) cmndash1

2983 2937 1741 1655 1514 1449 1370 1251 1207 1069 1029 MS (FAB) mz

542 (M+H) +

564 (M+Na) +


5422390 found

5422394


= -40 (c 0750 CHCl3) 1H-NMR (400

MHz CDCl3) 728ndash720 (3H m) 688 (16 H d J = 87 Hz) 680 (016 H d J = 87 Hz) 480ndash446 (m

494H) 438ndash387 (m 641 H) 380 (24 H s) 378 (06H s) 328 (06 H s) 327 (24 H s) 135ndash117

(9H m) 13

C-NMR (100 MHzCDCl3) 16830 16486 16440 16275 15921 13586 13336 12934

12846 12805 11404 11357 9957 6602 6214 6186 6140 5843 5551 5533 5527 5184 1400


2983 2938 2841 1742 1655 1514 1463 1372 1253 1211 1113 1068

1039 IR (neat) cm-1

2983 2938 1742 1655 1514 1463 1372 1253 1211 1113 1068 1039 MS (FAB)

mz 496 (M+H) +

518 (M+Na)+ 121 (base peak) HRMS (FAB) mz calcd for C24H34NO10 (M+H)

+ 4962183

found 4962182

41


= -47 (c 0597 CHCl3) 1H-NMR (400

MHz CDCl3) 758ndash711 (m 12H) 684 (d J = 92 Hz 16H) 674 (d J = 87 Hz 04H) 482 (d J =

169 Hz 08H) 476 (d J = 170 Hz 08H) 470 (dd J = 41 73 Hz 08H) 458 (d J = 32 Hz 02H)

454 (dd J = 50 82 Hz 02H)432ndash374 (m 112H) 131ndash124 (m 6H) 120 (t J = 73 Hz 24H) 111

(t J = 75 Hz 06H) 13

C-NMR (100 MHz CDCl3) 16849 16478 16449 16280 15911 13590

13559 13550 13296 13271 13264 12984 12979 12921 12831 12773 12770 11409 11385

11356 6255 6211 6176 6128 6007 5526 5159 2676 1907 1394 1388 IR (neat) cmndash1

2958

2933 2857 1739 1656 1514 1466 1426 1370 1252 1205 1178 1111 1069 1030 MS (FAB) mz 690

(M+H)+712 (M+Na)

+ 121 (base peak) HRMS (FAB) mz calcd for C38H48NO9Si(M+H)

+ 6903098 found

6903095

Synthesis of L-cysteine derivative 14

L-Cystein (10 g 83 mmol) was dissolved in t-BuOH (10 mL) 3N HCl (43 mL) After being stirred at

the reflux temperature for 11 h the solvent was evaporated under reduced pressure The resulting solid was

filtered with dry acetone to gave crude S6 (794 mg) To ethanol (234 mL) was added SOCl2 (034 mL 47

mmol) slowly at 0 oC After being stirred for 20 min at the same temperature to the mixture was added S6

(500 mg) and stirred at rt for 3 days The reaction mixture was concentrated to give a crude S7 which was

dissolved in MeOH (103 mL) and the resulting mixture was added p-anisaldehyde (0262 mL25 mmol)

After being sttired at the same temperature for 2 h to the mixture was added NaBH3CN (026 g 41 mmol)

After being stirred for 10 h at rt the reaction was quenched by addition of sat NaHCO3 and extracted with

AcOEt The extracts were washed with brine dried over MgSO4 filtered and concentrated The residual

brown oil was purified through silica gel column chromatography (AcOEtn-hexane = 37) to give S8 (162

mg 24) as a colorless oil

S8 colorless oil []D18

= -22 (c 0367 CHCl3) 1H-NMR (400 MHz CDCl3) 725(d J 87 Hz 2H)

685(d J 87 Hz 2H)421(q J 69 Hz 2H) 380ndash377(m 4H)366(d J Hz 1H) 346 (d J

64 Hz 1H) 284 (m 2H) 131ndash128 (m 12H) 13

C-NMR (100 MHz CDCl3) 17365 15879 13165

42

12958 11381 6101 6037 5531 5135 4233 3158 3094 1442 IR (neat) cmndash1

2962 2902 2836

1734 1612 1513 1462 1367 1300 1247 1178 1034 MS (FAB) mz 326 (M+H) +

348 (M+Na)+ 121 (base

peak) HRMS (FAB) mz calcd for C17H28NO3S (M+H) +

3261790 found 3261786

To a solution of S4 (60 mg 028 mmol) in CH2Cl2 (14 mL) were added oxalyl chloride (0076 mL 25

mmol) and DMF (1 drop) successively at rt After being stirred for 40 min the reaction mixture was

concentrated to give a crude S5 which was dissolved in CH2Cl2 (14 mL) and the resulting mixture was

added to a solution of S8 (60 mg 018 mmol) and i-Pr2NEt (0096 mL 055 mmol) in CH2Cl2 (14 mL) at 0

oC After being stirred for 30 min at the same temperature the reaction was quenched by addition of sat

NaHCO3 aq and extracted with CHCl3 The extracts were washed with brine and dried over Na2SO4

filtered and concentrated The residual brown oil was purified through silica gel column chromatography

(AcOEtn-hexane = 3565) to give 14 (57 mg 59) as a pale yellow oil

A 80 20 mixture of rotamers of 14 colorless oil []D18

= -56 (c 1287 CHCl3) 1H-NMR (400 MHz CDCl3)

754 (s 20100 H) 745ndash727 (m 240100 H) 722 (dd J = 87 Hz 40100 H) 689 (dd J = 87 Hz 160100H)

680 (dd J = 88 Hz 40100H) 473 (d J = 160 Hz 80100 H) 465 (d J =151 Hz 20100 H) 459 (d J =

165 Hz 80100 H) 453 (d J = 156 Hz 20100 H) 442 (t J = 74 Hz 20100 H) 437ndash394 (m 640100 H)

390ndash369 (m 340100H) 323 (dd J = 87 133 Hz 80100H) 309ndash299 (m 1 H) 278 (dd J = 78 138 Hz

20100 H) 136ndash108 (m 18 H) 13

C-NMR (100 MHz CDCl3) 16896 16881 16567 16548 16430 16426

16277 15941 15888 13613 13568 13426 13367 12964 12925 12879 12717 11399 11359 6215

6195 6186 6148 5987 5527 5266 4299 4285 3076 3065 2798 2764 1399 1391 1380 IR (neat)

cmndash1

2966 2904 2839 1734 1653 1514 1462 1369 1303 1253 1212 1069 1031 MS (FAB) mz 524

(M+H) +

546 (M+Na) +

121 (base peak) HRMS (FAB) mz calcd for C26H38NO8S (M+H) +

5242318 found

5242313

Typical Procedure of cyclization reaction of 4(Table 2-2 entry 1)

To a solution of 4 (79 mg 016 mmol) in dry EtOH (16 mL) was added Cs2CO3 (78 mg 024 mmol) at 20

˚C After being stirred for 10 h the reaction was quenched by addition of sat NH4Cl aq and extracted with

AcOEt The extracts were dried over Na2SO4 filtered and concentrated The residual oil was purified

through silica gel column chromatography (AcOEtn-hexane = 46) to give a diastereomeric mixture of 5a

5b and ethyl ether 6 (69 mg) 5a 5b and 6 were separated by Recycle HPLC (AcOEtn-hexane = 14 flow

= 30) to obtaine following chemical data

5a colorless oil HPLC conditions Daicel Chiralpak AD-H Hexane2-propanol = 91 flow = 09 mLmin

λ = 254 nm t=169 min t=232 min []D18

= -68 (c 0414 CHCl3 68 ee) 1H-NMR (400 MHz CDCl3)

43

734ndash716(m 7H)678(dd J 87 Hz 2H)462(d J 151 Hz 1H)446(d J 119 Hz

1H)428ndash420(m 2H) 411ndash403 (m 2H) 387(d J 96 Hz 1H)377(s3H) 364ndash355 (m 2H) 271

(dd J 46 179 Hz 1H) 246 (dd J 110 178 Hz 1H) 140 (s 3H) 124 (t 72 Hz 3H) 13

C-NMR

(100 MHz CDCl3) 16952 16947 16715 15882 13745 12993 12881 12829 12764 12741

11359 8131 7316 710 6719 6169 5522 5165 4505 3129 2793 1412 IR (neat) cmndash1

2979

2932 2867 1764 1735 1612 1514 1455 1392 1368 1247 1154 1032 MS (FAB) mz 498 (M+H) +

520

(M+Na) +


4982492 found 4982491

5b colorless oil Daicel Chiralpak AD-H Hexane2-propanol = 91 flow = 09 mLmin λ = 254 nm

t=165 min t=191 min []D18


736ndash715(m 7H)679(dd J 87 Hz 2H)445(d J 151 Hz 1H)434(d J 119 Hz 1H)429(d

J 151 Hz 1H)423(d J 119 Hz 1H)416ndash400(m 2H)377-373(m5H) 447 (d J 101 Hz

1H) 271 (d J 78 Hz 2H) 139 (s 3H) 119 (t J 74 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17033

16988 16774 15891 13718 13003 12837 12824 12778 12760 11363 8129 7337 6797 6447

6162 5523 5354 4480 3090 2788 1298 IR (neat) cmndash1

2979 2931 2869 1765 1732 1612 1514

1456 1391 1367 1248 1154 1097 1063 1031 MS (FAB) mz 498 (M+H) +

520 (M+Na) +

121 (base

peak) HRMS (FAB) mz calcd for C28H36NO7 (M+H) +

4982492 found 4982491

6a colorless oil HPLC conditions Daicel Chiralcel OD-H hexane2-propanol = 905 flow = 10 mLmin

λ = 230 nm t=252 min t=288 min 1H-NMR (400 MHz CDCl3) 726 (d J 82 Hz 2H) 683 (d J

87 Hz 2H) 464 (d J 151 Hz 1H) 429-421 (m 1H) 421 (d J 151 Hz 1H) 411-402 (m 1H)

383-375 (m 4H) 360 (dd J 110 46 Hz 1H) 351 (d J 96 Hz 1H) 328-317 (m 2H) 271 (dd J

174 41 Hz 1H) 245 (dd J 178 110 Hz 1H) 143 (s 9H) 124 (t J 76 Hz 3H) 110 (t J 73

Hz 3H) IR (neat) cmndash1

2983 2913 2845 1767 1735 1611 1588 1514 1453 1388 1247 1177 1105

1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +

121 (base peak) HRMS (FAB) mz calcd for C23H33NO7

(M+H) +

4362335 found 4362335

6b colorless oil HPLC conditions Daicel Chiralpak ID hexane2-propanol = 91 flow = 10 mLmin λ =

230 nm t=373 min t=433 min 1H-NMR (400 MHz CDCl3) 723 (d J 82 Hz 2H) 682 (d J 82

Hz 2H) 447 (d J 151 Hz 1H) 429 (d J 151 Hz 1H) 419-399 (m 2H) 379 (s 3H) 373 (dd J

92 69 Hz 1H) 368 (d J 101 Hz 1H) 354 (d J 101 Hz 1H) 329-323 (m 2H) 273ndash271 (m

2H) 143 (s 9H) 120 (t J 73 Hz 3H) 110 (t J 69 Hz 3H) 13


17003 16786 15895 13006 12829 11360 8126 6803 6678 6443 6156 5528 5350 4478

3092 2795 1489 1400 IR (neat) cmndash1

2976 2931 2873 1762 1734 1613 1514 1461 1390 1369

1292 1244 1152 1113 1064 1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +

121 (base peak) HRMS

(FAB) mz calcd for C23H33NO7 (M+H) +

4362335 found 4362335

44

Typical procedure for cyclization reaction in Table 2-3 entry 6 and Table 2-4

To a solution of 8 (80 mg 015 mmol) in CH3CN (074 mL) was added a solution of phenol (22 mg 015

mmol) in CH3CN (074 mL) and the resulting solution was cooled to -40 oC To the reaction solution was

added Cs2CO3 (98 mg 03 mmol) at -40 ˚C After being stirred for 24 h at the same temperature the

reaction was quenched by addition of sat NH4Cl aq and extracted with AcOEt The extracts were dried

over Na2SO4 filtered and concentrated The residual oil was purified through silica gel column

chromatography (AcOEtn-hexane = 14) to give a mixture of 8 9a and 9b 9a and 9b were separated by

Recycle HPLC (AcOEtn-hexane = 14 flow = 30) to give 9a (20 mg 25) and 9b (132 mg 17)

9a Daicel Chiralcel OD Hexane2-propanol = 91 flow = 10 mLmin λ = 254 nm t=184 min (minor)

t=453 min (major) colorless oil []D19

= -31 (c 0557 CHCl3 92 ee) 1H-NMR (400 MHz C6D6)

720ndash703 (m 7H) 667 (d J = 87 2H) 461 (d J = 151 Hz 1H) 436 (d J = 119 Hz 1H) 434 (d J =

151 Hz 1H) 421ndash407 (m 2H) 411 (d J = 119 Hz 1H) 403 (q J = 119 Hz 2H) 397 (d J = 108 Hz

1H) 394ndash380 (m 3H) 377-369 (m 1H) 350 (d J = 108 Hz 1H) 327 (s 3H) 104 (t J = 73 Hz 3H)

086 (t J = 69 Hz 3H) 081 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1696 1672 1668

1649 1594 1381 1303 1294 1285 1283 1278 1277 1139 733 711 667 623 619 616 548

547 501 453 1394 138 2 1382 IR (neat) cmndash1

2983 2935 2869 1766 1739 1612 1514 1456

1392 1369 1301 1249 1176 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +



5422390 found 5422400

9b Daicel Chiralcel OD Hexane2-propanol = 91 flow = 10 mLmin λ = 254 nm t=204 min (minor)

t=649 min (major)colorless oil []D19

= 19 (c 0920 CHCl3 92 ee) 1H-NMR (400 MHz C6D6) 710ndash700

(m 7H) 657 (d J = 87 Hz 2H) 465 (d J = 119 Hz 1H) 451 (d J = 119 Hz 1H) 433 (d J = 146 Hz 1H)

416 (d J = 151 Hz 1H) 417ndash404 (m 2H) 398 (q J = 124 Hz 2H) 386-359 (m 6H) 320 (s 3H) 099 (t

J = 73 Hz 3H) 078 (t J = 73 Hz 3H) 070 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1699 1677

1671 1657 1595 1376 1305 1286 1286 1283 12804 12800 1140 7344 6705 6415 6214 6178

6152 5673 5471 4943 4461 1397 1380 1370 IR (neat) cmndash1

2983 2935 2871 1769 1735 1612 1514

1458 1391 1369 1301 1249 1178 1098 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +

121 (base peak)

HRMS (FAB) mz calcd for C29H36NO9 (M+H) +

5422390 found 5422393

45

13a colorless oil Daicel Chiralpak AD-H Hexane2-propanol = 973 flow = 10 mLmin λ = 254 nm

t=180 min (minor) t=196 min (major) []D19

= -16 (c 0719 CHCl3 96 ee) 1H-NMR (400 MHz

CDCl3) 759(dd J = 46z 2H)(dd J z 2H)748-734(m 6H)708(d J 87 Hz

2H)672(d J 87 Hz 2H)450(d J = 151Hz 1H)433ndash421(m3H) 414ndash379 (m 8H) 375 (s

3H) 129 (t J =73 Hz 3H) 112 (t J =74 Hz 3H) 110 (t 73 Hz 3H) 106 (s 9H) 13

C-NMR (100

MHz CDCl3) 1692 1667 1666 1656 1589 1358 1357 1324 1300 1299 1278 1277 1137

668 633 621 620 617 552 529 492 449 268 192 1394 1380 137 IR (neat) cmndash1

2961

2934 2859 2369 2315 1769 1736 1650 1613 1514 1468 1428 1390 1370 1301 1251 1177 1108

1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +

121 (base peak) HRMS (FAB) mz calcd for

C38H48NO9Si (M+H) +

6903098 found 6903098


t=204 min (major) t=383 min (minor) []D19

= 9 (c 0511 CHCl3 92 ee) 1H-NMR (400 MHz CDCl3)

770 (dd J = 69 Hz 2H) 756ndash734 (m 8H) 678 (d J = 82 Hz 2H) 668 (d J = 83 Hz 2H) 461 (d J

= 151 Hz 1H) 444 (d J = 119 Hz 1H) 437ndash421 (m 2H) 420ndash404 (m 5H) 387ndash379 (m 1H) 373

(s 3H) 362ndash354 (m 1H) 345 (d J = 147 Hz 1H) 132 (t J = 73 Hz 3H) 120 (t J = 69 Hz 3H) 114

(s 9H) 099 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1695 1676 1670 1660 1589 1362

1357 1323 1318 1303 1300 1280 1278 1267 1136 639 6206 6202 614 597 552 483

441 269 190 1396 1392 136 IR (neat) cmndash1

2961 2934 2859 2369 2315 1769 1736 1650 1613

1514 1468 1428 1390 1370 1301 1251 1177 1108 1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


6903098 found 6903098

14 (50 mg 0096 mmol) and (CF3)2CHOH (16 mg 0096 mmol) in CH3CN (096 ml) which was babbled

46

with Ar for 20 min was treated with Cs2CO3 (62 mg 019 mmol) and stirred at 0 under Ar for 2 h The

reaction was quenched by addition of satNH4Cl The mixture was extracted with AcOEt (times3) The organic

extracts were washed with water brine dried over Na2SO4 filtered and concentrated The crude product

was purified by a silicagel column chromatography (AcOEtn-hexane = 3565) to give a 15a and 15b as a

diastereo mixture (43 mg 86 yield) 15a and 15b were separated by PTLC (AcOEttoluene = 1585)

15a colorless oil Daicel Chiralpak IC Hexane2-propanol = 11 flow = 10 mLmin λ = 230 nm t=139

min (minor) t=190 min (major) []D19


725 (d J = 96 Hz 2H) 682 (d J = 87 Hz 2H) 447 (d J = 151 Hz 1H) 427 (q J = 73 Hz 2H)

422ndash410 (m 4H) 406ndash396 (m 1H) 391ndash383 (m 1H) 381 (d J = 114 Hz 1H) 381 (d J = 114 Hz

1H) 378 (s 3H) 325 (d J = 128 Hz 1H) 305 (d J = 128 Hz 1H) 130 (t J = 71 Hz 3H) 130 (s 9H)

124 (t J = 68 Hz 3H) 114 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1697 1671 1666

1591 1304 1274 1137 655 622 6203 6196 555 553 493 453 427 320 307 139 138 IR

(neat) cmndash1

2966 2937 2868 1770 1734 1613 1514 1464 1389 1368 1301 1248 1178 1095 1033

MS (FAB) mz 524 (M+H) +

546 (M+Na) +

121 (base peak) HRMS (FAB) mz calcd for C26H38NO8S

(M+H) +

5242318 found 5242318

15b colorless oil Daicel Chiralcel OD-H Hexane2-propanol = 81 flow = 10 mLmin λ = 230 nm


= 24 (c 0551 CHCl3 91 ee) 1H-NMR (400 MHz

CDCl3) 725 (d J = 96 Hz 2H) 683 (d J = 87 Hz 2H) 450 (d J = 151 Hz 1H) 432ndash418 (m 7H)

410ndash402 (m 1H) 396ndash387 (m 1H) 378 (s 3H) 310 (d J = 124 Hz 1H) 287 (d J = 124 Hz 1H)

132 (t J = 68 Hz 3H) 127 (s 9H) 125 (t J = 74 Hz 3H) 116 (t J = 69 Hz 3H) 13

C-NMR (100 MHz

CDCl3) 1699 1672 1666 1654 1591 1303 1276 1137 643 6219 6219 6212 6198 560

553 485 453 428 303 291 140 138 IR (neat) cmndash1

2969 1769 1738 1613 1514 1464 1389

1369 1301 1248 1178 1034 MS (FAB) mz 690 (M+H) +

712 (M+Na) +

121 (base peak) MS (FAB)

mz 524 (M+H) +

546 (M+Na) +


5242318 found 5242313

Equiblirium experiment

To a solution of 9b (476 mg 0088 mmol 92 ee) in CH3CN (088 mL) was added

2222rsquo2rsquo2rsquo-hexafluoroisopropanol (93 μL 0088 mmol) and Cs2CO3 (573 mg 018 mmol) at -10 oC

The resulting mixture was stirred for 30 hr at the same temperatute and quenched by addition of sat NH4Cl

aq The aqueous layer was extracted with AcOEt and the extracts were dried over Na2SO4 filtered and

concentrated The residual oil was silica gel column chromatography (AcOEtn-hexane = 5050) to give a

diastereomeric mixture of 9b and 9a (quant dr=7822) The ee was determined by HPLC The ee of 9a was

92 and the ee of 9b was 92 respectively

The equilibrium experiment from 9a (392 mg 0072 mmol 92 ee) was performed as described above

Purification by silica gel column chromatography (AcOEtn-hexane = 5050) to give a diastereomeric

mixture of 9a and 9b (quant dr=7822) The ee was determined by HPLC The ee of 9a was 92 and the

47

ee of 9b was 89 respectively

Determination of the absolute configuration of 9

To a solution of 9 (40 mg 0074 mmol) in THF (037 mL) and water (037 mL) was added LiOHH2O (93

mg 022 mmol) at rt After being stitted at the same tempetature for 23 h to the reaction mixture was added

sat NaHCO3 aq and washed with Et2O The aqueous layer was acidified to pH 1~2 by addition of 1N HCl

aq and extracted with AcOEt (3 times) The organic layers were dried over Na2SO4 filtered and

concentrated to give a colorless solid (132 mg) to which solution in DMF (027 mL) was added

p-iodoaniline (177 mg 0081 mmol) WSCbullHCl (171 mg 0089 mmol) and HOBtbullanhydrous (131 mg

0097 mmol) and stirred at rt After being stirred for 4 h p-iodoaniline (118 mg 0054 mmol) was added

and stirred for 15 h The reaction was quenched by addition of sat NaHCO3 aq and extracted with AcOEt

(3 times) The organic layers were washed with 10 citric acid aq brine dried over Na2SO4 filtered and

concentrated The residue was purified by preparative TLC (SiO2 AcOEtn-hexane = 11) to give colorless

solid 16 16 was washed with Et2O and recrystallized from CH2Cl2hexane to give pure crystal 16 (6 mg)

Daicel Chiralpak IA Hexane2-propanol = 91 flow = 10 mLmin λ = 254 nm t=312 min (major) t=500

min (minor) 1H NMR (400MHz (CD3)2CO) 1064 (s 1H) 974 (s 1H) 775ndash770 (m 4H) 757 (d J

92 Hz 2H) 751 (d J 87 Hz 2H) 741 (d J 87 Hz 2H) 723ndash717 (m 5H) 688 (d 87 Hz 2H)

466 (d J = 151 Hz 1H) 459 (d J = 151 Hz 1H) 437ndash430 (m 2H) 399 (dd J = 32 119 Hz 1H)

389 (d J = 105 Hz 1H) 382 (d J = 101 Hz 1H) 380 (s 3H) 325 (dd J = 119 178 Hz 1H) 307 (dd

J = 32 179 Hz 1H) 13C-NMR (100 MHz CDCl3) 17051 16874 16770 15906 13787 13773 13743

13659 13031 12849 12833 12805 12760 12157 12144 11379 8783 8749 7347 6855 6695 5522

5203 4579 3189 HRMS (FAB) mz calcd for C34H31I2N3O5 (M+H) 8160432 found 8160430

Crystal data of 16 is as follows

Empirical formula C34 H31 I2 N3 O5

Formula weight 81542

Temperature 173(2) K

Wavelength 071069 Aring

Crystal system orthorhombic

Space group P212121 (19)

Unit cell dimensions a = 96903(7) Aring = 90deg

b = 120516(8) Aring = 90deg

c = 271658(19) Aring = 90deg

Volume 31725(4) Aring3

48

Z 4

Density (calculated) 1707 Mgm3

Absorption coefficient 2029 mm-1

F(000) 1608

Crystal size 050 x 030 x 010 mm3

Theta range for data collection 223 to 2550deg

Index ranges -11lt=hlt=9 -14lt=klt=11 -32lt=llt=32

Reflections collected 16475

Independent reflections 5791 [R(int) = 00608]

Completeness to theta = 2550deg 990

Max and min transmission 08229 and 04303

Refinement method Full-matrix least-squares on F2

Data restraints parameters 5791 0 398

Goodness-of-fit on F2 1021

Final R indices [Igt2sigma(I)] R1 = 00528 wR2 = 01203

R indices (all data) R1 = 00662 wR2 = 01299

Absolute structure parameter 004(3)

Largest diff peak and hole 1098 and -1059 eAring-3

49

22 Chepter 3

Procedure for synthesis of 20

To a solution of N-Boc-O-benzyl-L-threonine ethyl ester (19 g 55 mmol) in CH2Cl2 (28 mL) was added

trifluoroacetic acid (28 mL) at rt for 45 h The reaction mixture was concentrated to give a crude S9 which

was dissolved in EtOH (88 mL) To the resulting mixture was added p-anisaldehyde (064 mL53 mmol)

and 4 Aring morecular sieves (38 g) After being sttired at 50 oC for 22 h the reaction mixture was filtered and

concentrated The resulting residue was dissolved in MeOH (14 mL) and cooled to 0 oC To the solution

was added NaBH4 (034 g 893 mmol) and allowed to warm to rt After being stirred for 1 h the reaction

mixture was concentrated in vacuo The residual brown oil was purified through silica gel column

chromatography (AcOEtn-Hexane = 19 to 15) to give S10 (10 g 54) as a colorless oil


= -50 (c 1203 CHCl3) 1H-NMR (400 MHz CDCl3) 733ndash723 (m 7H) 684

(d J = 87 Hz 2H) 456 (d J = 119 Hz 1H) 443 (d J = 119 Hz 1H) 420ndash408 (m 2H) 389-384 (m

2H) 379 (s 3H) 358 (d J = 128 Hz 1H) 323 (d J = 41 Hz 1H) 219 (s 1H) 126 (d J = 64 Hz 3H)

122 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17340 15856 13834 13206 12945 12821

12758 12747 11357 7557 7075 6468 6064 5518 5170 1635 1421 IR (neat) cmndash1

2979 2932

2838 1734 1612 1512 1459 1373 1299 1247 1184 1159 1094 1032 MS (FAB) mz 358 (M+H) +

380 (M+Na) +


3582018 found

3582010

To a solution of S4 (363 mg 168 mmol) in CH2Cl2 (84 mL) was added oxalyl chloride (046 mL 42


concentrated to give a crude S5 which was dissolved in CH2Cl2 (7 mL) The resulting mixture was added

to a solution of S10 (500 mg 14 mmol) and i-Pr2NEt (073 mL42 mmol) in CH2Cl2 (7 mL) at rt After

being stirred for 30 min at the same temperature the reaction was quenched by addition of sat NaHCO3

and extracted with CHCl3 The extracts were washed with brine and dried over Na2SO4 filtered and

concentrated The residual brown oil was purified through silica gel column chromatography

(AcOEtn-hexane = 3565) to give 20 (056 g 72) as a pale yellow oil



750 (s 028H) 736ndash723 (m 644H) 717 (d J = 87 Hz 056H) 712 (s 072H) 682 (d J = 87 Hz

144 H) 673 (d J = 87 Hz 056 H) 488 (d J = 64 Hz 072 H) 483 (d J = 165 Hz 072 H) 464-454

(m 172H) 451 (d J = 115 Hz 028 H) 445 (d J = 151 Hz 028 H) 439ndash394 (m 772H) 382ndash372

(m 356H) 133ndash118 (m 1115H) 111 (t J = 76 Hz 084 H) 13

C-NMR (100 MHzCDCl3) 16888

50

16816 16636 16551 16455 16405 16302 16273 15888 15856 13824 13766 13612 13528

13398 13306 13096 12955 12945 12878 12832 12827 12809 12767 12757 12751 12726

12660 11377 11329 7416 7161 7135 7080 6563 6221 6195 6167 6118 5517 7167 1732

1663 1393 1385 1370 IR (neat) cmndash1

2981 2936 2905 1738 1652 1513 1457 1372 1250 1205

1177 1096 1067 1030 MS (FAB) mz 556 (M+H)+ 578 (M+Na)

+ 121 (base peak) HRMS (FAB) mz calcd

for C30H38NO9 (M+H) +

5562547 found 5562547


To a stirred solution of N-Boc-L-allo-throenine (800 mg 37 mmol) in DMF (61 mL) was slowly added

sodium hydride in 60 oil suspension (336 mg 84 mmol) at -5 oC The reaction mixture was stirred at the

same temperature After the generation of the H2 gas was stopped to the reaction mixture was slowly and

carefully added benzylbromide (052 mL 44 mmol) at the same temperature After being stirred for 7 h at

the same temperature the reaction mixture was poured into ice-water and washed with Et2O (times1) After the

aqueous phase was acidified to pH 1 by addition of 1 N HCl aq the resulting solution was extracted with

AcOEt (times3) The combined organic layers were washed with water brine dried over Na2SO4 filtered and

concentrated to give the crude product of S11 which was dissolved in CH2Cl2 (127 mL) To the resulting

solution was added EtOH (074 mL 127 mmol) WSCbullHCl (729 mg 127 mmol) DMAP (309 mg 025

mmol) i-Pr2NEt (044 mL 25 mmol) at rt After being stirred for 25 h at the same temperature the

reaction was quenched by addition of sat NaHCO3 aq and extracted with CHCl3 (times3) The extracts were

washed with 10 citric acid aq water brine dried over Na2SO4 filtered and concentrated The residual oil

was purified by silica gel column chromatography (AcOEtn-Hexane = 15) to give ethyl ester S12 (645 mg

57 in 2 steps) To a solution of S12 in CH2Cl2 (96 mL) was added trifluoroacetic acid (96 mL) at rt

After being stirred for 50 min at the same temperature the solvent was removed in vacuo to give the crude

product of S13 To a solution of a crude product of S13 (350 mg 10 mmol) in dry EtOH (50 mL) was

added p-anisaldehyde (012 mL 10 mmol) 3Aring MS and diisopropylethylamine (017 mL 10 mmol) at rt

and stirred at 50 oC After being stirred at the same temperature for 195 h the reaction mixture was cooled

to 0 oC and NaBH4 (64 mg 17 mmol) was slowly added and stirred at rt After being stirred at the same

temperature for 15 h the solvent was removed in vacuo To the residual mixture was added water and

extracted with AcOEt (times3) The extracts were washed with water brine dried over Na2SO4 filtered and

51

concentrated The residual oil was purified by silica gel column chromatography (AcOEtn-Hexane =

19~15) to give S14 (193 mg 54) as a colorless oil



(d J = 87 Hz 2H) 453 (d J = 119 Hz 1H) 439 (d J = 114 Hz 1H) 419 (q J = 69 Hz 2H)

382-370 (m 5H) 359 (d J = 128 Hz 1H) 334 (d J = 59 Hz 1H) 195 (s 1H) 127ndash124 (m 6H)

13C-NMR (100 MHz CDCl3) 17382 15864 13832 13180 12947 12821 12747 11365 7634

7091 6465 6065 5522 5147 1657 1431 IR (neat) cmndash1

2979 2933 2837 1730 1611 1513 1460

1372 1302 1247 1185 1108 1033 MS (FAB) mz 358 (M+H) +

380 (M+Na) +



3582018 found 3582023

To a solution of carboxylic acid S4 (87 mg 040 mmol) in CH2Cl2 (20 mL) was added oxalyl chloride

(011 mL 10 mmol) and DMF (1 drop) successively at rt After being stirred for 40 min the reaction

mixture was concentrated to give a crude acid chloride S5 which was dissolved in CH2Cl2 (19 mL) and

the resulting mixture was added to a solution of S14 (120 mg 034 mmol) and i-Pr2NEt (018 mL10

mmol) in CH2Cl2 (15 mL) at 0 oC After being stirred for 30 min at the same temperature the reaction was

quenched by addition of sat NaHCO3 aq and extracted with CHCl3 The extracts were washed with brine

dried over Na2SO4 filtered and concentrated The residual brown oil was purified by silica gel column

chromatography (AcOEtn-hexane = 28) and PTLC (AcOEttoluene = 1585) to give 26 (128 mg 68) as

a colorless oil

26 colorless oil []D18

= -46 (c 1700 CHCl3) 1H-NMR (400 MHz (CD3)SO 130

oC) 737ndash720 (m

7H) 693ndash691 (m 2H) 471ndash444 (m 5H) 427ndash422 (m 5H) 409ndash402 (m 2H) 381ndash377 (m 3H)

131ndash115 (m 12H) 13

C-NMR (100 MHz CDCl3) 16879 16872 16586 16491 16444 16396

16272 15920 15885 13827 13754 13584 13551 13513 13355 12972 12894 12852 12837

12824 12798 12787 12778 12749 11403 11355 7490 7341 7219 7117 6505 6219 6214

6185 6151 6112 5525 5520 5151 1641 1619 1397 1386 IR (neat) cmndash1

2982 2937 2905

1739 1656 1613 1513 1450 1373 1252 1203 1095 1070 1030 MS (FAB) mz 556 (M+H) +

578

(M+Na)+ 121 (base peak) HRMS (FAB) mz calcd for C30H38NO9 5562547 (M+H)

+ found 5562549

Cyclization reaction of L-threonine derivative 20 and L-allo-threonine derivative 26

20 (43 mg 0078 mmol) and (CF3)2CHOH (13 mg 0078 mmol) in CH3CN (078 ml) was treated with

Cs2CO3 (51 mg 016 mmol) and stirred at 0 oC under Ar for 24 h The reaction was quenched by addition

of satNH4Cl The mixture was extracted with AcOEt (times3) The organic extracts were washed with water

52

brine dried over Na2SO4 filtered and concentrated The crude product was purified by PTLC (AcOEt

n-hexane = 3565) to give 21a (294 mg 68) and 21b (45 mg 10)

21a colorless oil []D19

= -24 (c 0932 CHCl3) 1H-NMR (400 MHz C6D6) 726 (d J = 87 Hz 2H)

718ndash712 (m 4H) 709ndash705 (m 1H) 669 (d J = 87 Hz 2H) 487 (d J = 160 Hz 1H) 447 (d J = 110

Hz 1H) 436 (d J = 160 Hz 1H) 423 (d J = 119 Hz 1H) 423ndash410 (m 2H) 404ndash391 (m 4H)

390ndash381 (m 2H) 378 (q J = 69 Hz 1H) 328 (s 3H) 119 (d J = 64 Hz 3H) 105 (t J = 73 Hz 3H)

094 (t J = 74 Hz 3H) 085 (t J = 74 Hz 3H) 13

C-NMR (100 MHz C6D6) 1702 1677 1673 1663

1598 1395 1308 1303 1290 1289 1281 1279 1145 784 716 713 628 625 621 5529

5526 513 465 161 1454 1450 1445 IR (neat) cmndash1

2981 2925 1766 1739 1648 1612 1514

1461 1390 1371 1301 1249 1178 1096 1031 MS (FAB) mz 556 (M+H) +



5562547 found 5562545

21b colorless oil []D19

= 43 (c 040 CHCl3) 1H-NMR (400 MHz C6D6) 738 (d J = 87 H 2H)

724ndash705 (m 5H) 669 (d J = 87 Hz 2H) 480 (d J = 146 Hz 1H) 436 (q J = 64 Hz 1H) 430 (d J

= 151 Hz 1H) 425 (d J = 119 Hz 1H) 425ndash409 (m 2H) 410 (d J = 115 Hz 1H) 402 (d J = 115

Hz 1H) 397 (q J = 69 Hz 2H) 393 (d J = 115 Hz 1H) 387ndash379 (m 2H) 324 (s 3H) 106 (t J =

73 Hz 3H) 091 (t J = 69 Hz 3H) 082 (d J = 64 Hz 3H) 080 (t J = 73 Hz 3H) 13

C-NMR (100

MHz C6D6) 1707 1671 1667 1651 1593 1387 1312 1300 1285 1283 1277 1276 1138 766

719 716 624 619 616 546 542 505 466 140 139 124 IR (neat) cmndash1

2983 2938 1766 1739

1613 1514 1459 1373 1248 1177 1148 1097 1032 MS (FAB) mz 556 (M+H) +

121 (base peak)


5562547 found 5562549

21c white crystal 1H-NMR (400 MHz CDCl3) 736ndash722 (m 7H) 675 (d J = 87 Hz 2H) 463 (d J =

160 Hz 1H) 438 (d J = 110 Hz 1H) 436 (d J = 110 Hz 1H) 429ndash410 (m 9H) 407 (d J = 119 Hz

1H) 377 (s 3H) 129ndash125 (m 6H) 123 (t J = 73 Hz 3H) 116 (d J = 64 Hz 3H) 13

C-NMR (100

MHz CDCl3) 17035 16717 16663 16632 15871 13750 12961 12854 12832 12772 12766

11357 7216 7007 6893 6202 6187 5606 5520 4872 4588 1547 1403 1399 1396 IR (neat)

cmndash1

2983 2914 2845 1767 1735 1611 1588 1514 1453 1388 1248 1177 1105 1032 MS (FAB)

mz 556 (M+H) +


5562547 found

5562546

Cyclization reaction from 26 (70 mg 0126 mmol) was performed as described above Purification by

PTLC (AcOEtn-hexane = 3565) to give ent-21b (574 mg 82) and ent-21a (18 mg 25)

53

Determination of absolute configuration of 21a

To a solution of 21a (921 mg 166 mmol) in CH3CN (166 mL 01 M) was added N-phenylthio-

succinimide (522 mg 15 eq) and K2CO3 (310 mg 14 ed) The reaction mixture was stirred at rt After

being stirred for 30 min the reaction mixture was poured into water and extracted with AcOEt (times3) The

extracts were dried over Na2SO4 filtered and concentrated in vacuo to give a crude 22 which was

dissolved in CH2Cl2 (146 mL 01 M) and cooled to 0 oC To the solution was added m-chloroperbenzoic

acid (277 mg 16 mmol) The reaction was allowed to warm to rt and stiired at the same temperature After

being stirred for 30 min the reaction mixture was poured into sat NaHCO3 aq and extracted with CHCl3

(times3) The extracts were dried over Na2SO4 filtered and concentrated in vacuo The residual oil was

dissolved in toluene (146 mL 01 M) After being stirred at the reflux temperature for 2 h the reaction

mixture was cooled to rt and the solvent was removed in vacuo The residual oil was purified by silica gel

column chromatography (AcOEtn-hexane = 2575~3070) to afford 23 as a colorless oil (548mg 60

yield in 3 steps) To a solution of LiOHH2O ( 454 mg 30 eq) in H2O (36 mL) was added a solution of

23 (200 mg 036 mmol) in THF (36 mL) and stirred at rt After being stirred for 17 h at the same

temperatuture the reaction solution was acidified to pH 1~2 by addition of 1 N HCl aq The resulting

mixture was extracted with AcOEt (times3) The extracts were dried over Na2SO4 filtered and concentrated in

vacuo to afford the tricarboxylic acid 24 (178 mg) To a solution of 24 (169 mg 036 mmol) in CH2Cl2 (36

mL) were added oxalyl chloride (016 mL 14 mmol) and DMF (1 drop) successively at rt After being

stirred for 40 min the reaction mixture was concentrated to give a crude acid chloride which was dissolved

in CH2Cl2 (18 mL) and cooled to 0 oC To the resulting solution was added a solution of p-iodoaniline (261

54

mg 12 mmol 30 eq) and i-Pr2NEt (025 mL 14 mmol 40 eq) in CH2Cl2 (18 mL) at 0 oC After being

stirred for 20 min at rt the reaction was quenched by addition of sat NaHCO3 and extracted with CHCl3

(times3) The extracts were washed with brine dried over Na2SO4 filtered and concentrated The crude product

was purified through silica gel column chromatography (AcOEtn-hexane = 2080~2575) to give 25 (114

mg 29) as a yellow needle The needle was recrystallized from CH2Cl2toluenen-Hexane to obtain the

crystalline solid for X-ray crystallography

25 yellow crystal 1H-NMR (400 MHz CDCl3) 1138 (s 1H) 1107 (s 1H) 1095 (s 1H) 785ndash762 (m

6H) 746ndash735 (m 6H) 729 (d J = 55 Hz 2H) 719ndash715 (m 3H) 701 (d J = 41 Hz 2H) 683 (d J =

59 Hz 2H) 513 (d J = 106 Hz 1H) 492 (d J = 105 Hz 1H) 459 (q J = 46 Hz 1H) 445 (d J = 78

Hz 1H) 420 (d J = 78 Hz 1H) 379 (s 3H) 118 (d J = 41 Hz 3H) IR (neat) cmndash1

3033 2359 2306

1737 1677 1610 1585 1537 1516 1486 1394 1322 1248 1179 1117 1061 1033 1006 MS (FAB) mz

1095 (M+Na) +

154 (base peak) HRMS (FAB) mz calcd for C42H35N4O6NaI3 (M+Na) +

10949589 found

10949577


Empirical formula C42 H35I3 N 4O6 05 (C7H8) 05 (CH2Cl2)





Space group C2221


b = 30665(2) Aring = 90deg

c = 134874(12) Aring = 90deg


Z 8



F(000) 4544











55





Crystal data of 21c is as follows

Empirical formula C30 H37 N O9




Crystal system monoclinic

Space group C2(5)


b = 75202(3) Aring = 1025865(14)deg

c = 236650(9) Aring = 90deg


Z 8



F(000) 2368













Absolute structure parameter -08(11)


56

23 Chapter 4

Preparation of 3-vinylcyclopent-2-en-1-one 27 37

Iodine (47 mg 018 mmol) was added to a solution of 13-cyclopentanedione (600 mg 612 mmol) in

methanol (12 mL) at room temperature and stirred at the same temperature After 48 h the resulting

solution was concentrated in vacuo The residual oil was purified by silica gel column chromatography

(AcOEtn-hexane = 31~10) to afford 3-methoxycyclopent-2-en-1-one as a light yellow solid (546 mg

80 yield) To a solution of 3-methoxycyclopent-2-en-1-one (458 mg 36 mmol 10 equiv) in THF (40

mL 40 mmol) was added dropwise a solution of a vinyl magnesium bromide (1 M in THF 11 equiv) at

0 degC under argon Once the addition was complete the resulting solution was allowed to warm to room

temperature and stirred for 30 min The reaction mixture was poured into 1 N HCl aq at 0 degC The layers

were separated and the aqueous layer was extracted with AcOEt (3times20 mL) The combined organic layers

were washed successively with brine dried over Na2SO4 filtered and concentrated under reduced pressure

The crude product was purified by silica gel column chromatography (AcOEtn-hexane = 2872) to afford

27 as a colorless oil (267mg 68 yield)

colorless oil IR (neat) cmndash1

3560 3092 3010 2924 1706 1673 1627 1573 1440 1410 1346 1290

1177 1H NMR (400 MHz CDCl3) 684 (1H dd J=178 Hz 110 Hz) 607 (1H s) 580 (1H d J=174

Hz) 556 (1H d J=106 Hz) 278ndash276 (2H m) 249-247 (2H m) 13

C NMR (100 MHz CDCl3)

20959 17198 13272 13104 12237 3465 2642 MS (ESI) mz 109 ([M+H]+) HRMS (ESI) mz

calcd for C7H9O [M+H]+ 1090648 found 1090650

General procedure for preparation of N-sulfonyl imines 28 38

N-sulfonyl imines 28 were prepared according to the literature procedures36

A mixture of aldehyde (10

eq) p-toluenesufonamide (10 eq) and tetraethoxysilane (105 eq) was heated at 160 degC for 4-6 h and

then cooled to room temperature The resulting mixture was crystallized with AcOEt and n-hexane (101 to

11) and the resulting solid was collected by filtration dried in vacuum to afford N-sulfonylimines 28

57

Typical procedure for preparation of aza-MBH adducts at α-position 4-Methyl-N-[(5-oxo-2-

vinylcyclopent-1-en-1-yl)(phenyl)methyl]benzenesulfonamide 29a (Table 4-1 entry 3)

A mixture of 27 (54 mg 005 mmol) 28a (259 mg 010 mmol) DABCO (54 mg 005 mmol) in MeOH

(02 mL 025 M) was stirred at 20 oC for 24 h A solvent was evaporated in vacuo The yield of 3a was

determined by 1H NMR integration with dinitrobenzene (84 mg 005 mmol) as an internal standard (

1H

NMR yield 29aquant 30a0) The crude oil was purified by PTLC (dioxanen-hexane = 46) to give 29a

as a colorless needle (173 mg 92)

29a white solid mp 123ndash125 ˚C IR (KBr) cmndash1

3298 3058 2958 1678 1629 1581 1448 1419 1358

1338 1305 1166 1089 1061 1H NMR (400 MHz CDCl3) 756 (2H d J=82 Hz) 728ndash718 (5H m)

714 (2H d J=82 Hz) 690 (1H dd J=174 Hz 110 Hz) 663 (1H d J=101 Hz) 579 (1H d J=170

Hz) 567 (1H d J=110 Hz) 553 (1H d J=101 Hz) 264ndash253 (1H m) 237 (3H s) 225ndash217 (2H m)

194ndash187 (1H m) 13

C NMR (100 MHz CDCl3) 20910 16553 14294 13841 13754 13634

12973 12914 12858 12767 12711 12640 12437 5337 3368 2522 2142 MS (ESI) mz 390

([M+Na]+) HRMS (ESI) mz calcd for C21H21NNaO3S [M+Na]

+ 3901134 found 3901138

Typical Procedure for preparation of aza-MBH adducts at γ-position

4-methyl-N-(2-(3-oxocyclopent-1-en-1-yl)-1-phenylallyl)benzenesulfonamide 30a (Table 4-1 entry 11)

A mixture of 27 (54 mg 005 mmol) 28a (259 mg 010 mmol) DMAP (61 mg 005 mmol) in CHCl3

(02 mL 025 M) was stirred at 20 oC for 24 h The solvent was evaporated in vacuo The yield of 29a and

30a was determined by 1H NMR integration with dinitrobenzene (84 mg 005 mmol) as an internal

standard (1H NMR Yield 29a9 30a81) The crude oil was purified by PTLC (AcOEtn-hexane =

3565) to give pure 30a (149 mg 81) and not pure 29a The pure 29a was obtained after PTLC

separation (14-dioxanen-hexane = 46) as a colorless needle (22 mg 12)

30a colorless oil IR (neat) cmndash1

3265 3028 2924 1676 1573 1494 1449 1330 1190 1159 1088 1H

NMR (400 MHz CDCl3) 766 (2H d J=82 Hz) 728ndash717 (5H m) 697ndash694 (2H m) 589 (1H s)

584 (1H s) 580 (1H t J=14 Hz) 519 (1H d J=69 Hz) 503 (1H d J=69 Hz) 282ndash263 (2H m)

245ndash228 (5H m) 13

C NMR (100 MHz CDCl3) 20938 17011 14378 14253 13821 13688 12966

12943 12908 12843 12727 12699 12155 5944 3429 2837 2156 MS (ESI) mz 390 ([M+Na]+)

58

HRMS (ESI) mz calcd for C21H21NNaO3S [M+Na]+ 3901134 found 3901141

General procedure for Table 4-2

Condition A To a stirred solution of 27 (10 eq) and 28 (20 eq) in the appropriate solvent (02 mL 025

M) was added DABCO (10 eq) at 20 ˚C and stirred at the same temperature The reaction mixture was

concentrated in vacuo The resulting residual oil was purified through PTLC (14-dioxanen-hexane) to give

29

Condition B To a stirred solution of 27 (10 eq) and 28 (20 eq) in CHCl3 (02 mL 025 M) was added

DMAP (10 eq) at 20 ˚C and stirred at the same temperature The mixture was concentrated in vacuo The

resulting residual oil was purified through PTLC (AcOEtn-hexane or 14-dioxanen-hexane) to give 29 and

30 respectively

29b white solid mp 203ndash206 ˚C IR (KBr) cmndash1

3276 1684 1631 1599 1518 1432 1348 1162 1089

1061 1H NMR (400 MHz CDCl3) 809 (2H d J=92 Hz) 757 (2H d J=82 Hz) 741 (2H d J=82

Hz) 716 (2H d J=82 Hz) 690 (1H dd J=174 Hz 110 Hz) 665 (1H d J=101 Hz) 587 (1H d

J=170 Hz) 575 (1H d J=110 Hz) 559 (1H d J=101 Hz) 269ndash262 (1H m) 238 (3H s) 231ndash222

(2H m) 205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20885 16645 14728 14557 14346

13728 13533 12935 12922 12736 12703 12552 12378 5275 3364 2545 2144 MS (FAB) mz

435 ([M+Na]+) 413 ([M+H]

+) 154 (base peak) HRMS (FAB) mz calcd for C21H20N2NaO5S [M+Na]

+

4350991 found 4350991

29c colorless oil IR (neat) cmndash1

3276 2928 1683 1631 1584 1511 1432 1335 1307 1249 1165 1092

1033 1H NMR (400 MHz CDCl3) 755 (2H d J=82 Hz) 715 (4H d J=87 Hz) 688 (1H dd J=174

Hz 110 Hz) 676 (2H d J=87 Hz) 658 (1H d J=101 Hz) 578 (1H d J=165 Hz) 565 (1H d J=105

59

Hz) 547 (1H d J=101 Hz) 375 (3H s) 260ndash254 (1H m) 237 (3H s) 225ndash216 (2H m) 193ndash186

(1H m) 13

C NMR (100 MHz CDCl3) 20919 16528 15904 14286 13759 13653 13058 12975

12912 12769 12714 12422 11392 5523 5299 3372 2519 2141 MS (FAB) mz 420 ([M+Na]+)

154 (base peak) HRMS (FAB) mz calcd for C22H23NNaO4S [M+Na]+ 4201245 found 4201239

29d colorless oil IR (neat) cmndash1

3269 2922 1684 1630 1583 1491 1426 1338 1162 1091 1H NMR

(400 MHz CDCl3) 755 (2H d J=82 Hz) 720ndash715 (6H m) 688 (1H dd J=170 Hz 105 Hz) 660

(1H d J=101 Hz) 581 (1H d J=170 Hz) 569 (1H d J=114 Hz) 549 (1H d J=101 Hz) 263ndash257

(1H m) 238 (3H s) 226ndash220 (2H m) 198ndash191 (1H m) 13

C NMR (100 MHz CDCl3) 20905

16579 14313 13747 13695 13600 13362 12952 12922 12872 12785 12709 12477 5285

3370 2529 2144 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]

+ base peak) HRMS (ESI) mz calcd

for C21H20ClNNaO3S [M+Na]+ 4240745 found 4240733

29e colorless oil IR (neat) cmndash1

3272 2921 1684 1630 1428 1338 1162 1092 1H NMR (400 MHz

CDCl3) 756 (2H d J=82 Hz) 714 (2H d J=77 Hz) 712 (2H d J=82 Hz) 705 (2H d J=77 Hz)

690 (1H dd J=174 Hz 105 Hz) 659 (1H d J=101 Hz) 577 (1H d J=174 Hz) 565 (1H d J=110

Hz) 549 (1H d J=101 Hz) 260ndash254 (1H m) 237 (3H s) 228 (3H s) 225ndash217 (2H m) 193ndash186

(1H m) 13

C NMR (100 MHz CDCl3) 20913 16534 14287 13759 13747 13651 13548 12978

12926 12912 12714 12633 12421 5321 3370 2520 2142 2098 MS (ESI) mz 404 ([M+Na]+

base peak) HRMS (ESI) mz calcd for C22H23NNaO3S ([M+Na]+) 4041296 found 4041281

29f colorless oil IR (KBr) cmndash1

3273 2922 1685 1630 1585 1488 1426 1338 1071 1011 1H NMR

(400 MHz CDCl3) 754 (2H d J=82 Hz) 735 (2H d J=82 Hz) 715 (2H d J=82 Hz) 710 (2H d

J=87 Hz) 687 (1H dd J=174 Hz 106 Hz) 661 (1H d J=96 Hz) 581 (1H d J=169 Hz) 569 (1H d

60

J=110 Hz) 547 (1H d J=101 Hz) 263ndash256 (1H m) 238 (3H s) 227ndash220 (2H m) 199ndash192 (1H

m) 13

C NMR (100 MHz CDCl3) 20906 16581 14315 13748 13745 13593 13166 12951

12923 12818 12708 12481 12176 5292 3370 2529 2145 MS (FAB) mz 470 ([M+2+Na]+ base

peak) 468 ([M+Na]+) 448 ([M+2+H]) 446 ([M+H]) HRMS (FAB) mz calcd for C21H20BrNNaO3S

[M+Na]+ 4680245 found 4682045

29g colorless oil IR (neat) cmndash1

3271 2923 1687 1630 1585 1425 1328 1163 1121 1068 1018 1H

NMR (400 MHz CDCl3) 754 (2H d J=82 Hz) 747 (2H d J=87 Hz) 734 (2H d J=83 Hz) 713

(2H d J=82 Hz) 691 (1H dd J=170 Hz 106 Hz) 670 (1H d J=101 Hz) 584 (1H d J=174 Hz)

572 (1H d J=110 Hz) 557 (1H d J=97 Hz) 266ndash259 (1H m) 236 (3H s) 231ndash218 (2H m)

205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20904 16607 14322 14234 13740 13574

12986 (q J=324 Hz) 12939 12924 12703 12683 12552 (q J=27 Hz) 12506 12385 (q J=2708

Hz) 5310 3368 2535 2137 MS (FAB) mz 458 ([M+Na]+) 436 ([M+H]

+) 265 (base peak) HRMS

(FAB) mz calcd for C22H20F3NNaO3S ([M+Na]+) 4581014 found 4581020

29h colorless oil IR (neat) cmndash1

3267 1685 1631 1594 1434 1339 1162 1092 1H NMR (400 MHz

CDCl3) 755 (2H d J=87 Hz) 718ndash711 (6H m) 687 (1H dd J=174 Hz 105 Hz) 662 (1H d

J=101 Hz) 583 (1H d J=174 Hz) 570 (1H d J=106 Hz) 548 (1H d J=99 Hz) 266ndash259 (1H m)

238 (3H s) 229ndash221 (2H m) 199ndash192 (1H m) 13

C NMR (100 MHz CDCl3) 20900 16598

14315 14039 13741 13579 13450 12985 12948 12923 12788 12705 12660 12489 12462

5290 3368 2532 2143 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]

+ base peak) HRMS (ESI) mz

calcd for C21H20ClNNaO3S [M+Na]+ 4240745 found 4240736

29i white solid mp 153ndash155 ˚C IR (KBr) cmndash1

3261 1692 1630 1581 1491 1427 1342 1321 1162

61

1041 1H NMR (400 MHz CDCl3) 756 (2H d J=82 Hz) 722ndash710 (4H m) 706ndash701 (2H m) 681

(1H dd J=174 Hz 106 Hz) 640 (1H d J=101 Hz) 574 (1H d J=170 Hz) 571 (1H d J=92 Hz)

562 (1H d J=105 Hz) 260ndash245 (1H m) 252 (3H s) 238 (3H s) 229ndash214 (2H m) 181ndash173 (1H

m) 13

C NMR (100 MHz CDCl3) 20965 16573 14293 13732 13644 13635 13629 13093

13990 12901 12811 12740 12734 12617 12420 5106 3372 2528 2144 1981 MS (FAB) mz

404 ([M+Na]+) 382 ([M+H]

+) 211 (base peak) HRMS (FAB) mz calcd for C22H23NNaO3S ([M+Na]

+)

4041296 found 4041296

30b pale yellow solid mp 167ndash171 ˚C IR (neat) cmndash1

3265 2925 1698 1677 1575 1522 1442 1346

1160 1089 1H NMR (400 MHz CDCl3) 808 (2H d J=87 Hz) 763 (2H d J=82 Hz) 726ndash725 (4H

m) 587 (1H s) 578 (1H s) 558 (1H s) 538 (1H d J=69 Hz) 519 (1H d J=73 Hz) 280ndash262 (2H

m) 244 (3H s) 241ndash237 (2H m) 13

C NMR (100 MHz CDCl3) 20879 16906 14755 14539

14435 14204 13663 12977 12970 12805 12716 12403 12280 5878 3433 2834 2156 MS

(ESI) mz 435 ([M+Na]+ base peak) HRMS (ESI) mz calcd for C21H20N2NaO5S [M+Na]

+ 4350985

found 4350980


3263 2925 1702 1676 1611 1574 1512 1442 1329 1253 1159 1088


Hz) 672 (2H d J=87 Hz) 589 (2H s) 576 (1H s) 511 (1H d J=60 Hz) 472 (1H d J=64 Hz) 375

(3H s) 284ndash265 (2H m) 247 (3H s) 243ndash229 (2H m) 13

C NMR (100 MHz CDCl3) 20939 17019

15960 14381 14266 13687 13026 12972 12942 12828 12731 12116 11446 5895 5527

3429 2841 2159 MS (ESI) mz 420 ([M+Na]+ base peak) HRMS (ESI) mz calcd for C22H23NNaO4S

[M+Na]+ 4201240 found 4201233

62

30d pale yellow solid mp 58ndash61 ˚C IR (neat) cmndash1

3262 2923 1677 1575 1491 1441 1333 1160

1090 cm-1

1H NMR (400 MHz CDCl3) 764 (2H d J=82 Hz) 727 (2H d J=87 Hz) 718 (2H d

J=87 Hz) 691 (2H d J=82 Hz) 587 (1H s) 578 (1H s) 574 (1H s) 520 (1H d J=68 Hz)

497ndash487 (1H br s) 282ndash262 (2H m) 246 (3H s) 241ndash231 (2H m) 13


20924 16980 14391 14234 13684 13672 13423 12966 12951 12910 12845 12716 12285

5874 3429 2835 2155 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3265 2924 1698 1677 1574 1442 1332 1188 1160 1089 1043 1H


(2H d J=82 Hz) 589 (1H s) 588 (1H s) 578 (1H s) 512 (1H d J=64 Hz) 491 (1H br d J=55 Hz)

282ndash264 (2H m) 246 (3H s) 241ndash228 (2H m) 227 (3H s) 13


17021 14375 14261 13839 13688 13528 12976 12966 12940 12729 12689 12128 5922

3428 2838 2157 2101 MS (ESI) mz 404 ([M+Na]+ base peak) HRMS (ESI) mz calcd for

C22H23NNaO3S [M+Na]+ 4041291 found 4041284

30f colorless oil IR (neat) cmndash1

3262 3022 2871 1698 1677 1575 1488 1441 1404 1333 1160


Hz) 685 (2H d J=82 Hz) 587 (1H s) 580 (1H s) 574 (1H s) 519 (1H d J=69) 493 (1H d J=69)

282ndash262 (2H m) 246 (3H s) 241ndash230 (2H m) 13

C NMR (100 MHz CDCl3) 20914 16969

14398 14229 13723 13680 13211 12970 12955 12875 12719 12244 12187 5884 3429

2836 2158 MS (ESI) mz 470 ([M+2+Na]+ base peak) 468 ([M+Na]

+) HRMS (ESI) mz calcd for

C21H20BrNNaO3S [M+Na]+ 4680239 found 4682035

63

30g white solid mp 162ndash165 ˚C IR (neat) cmndash1

3261 2927 1698 1677 1620 1575 1442 1327 1161

1122 1068 1018 1H NMR (400 MHz CDCl3) 761 (2H d J=87 Hz) 745 (2H d J=83 Hz) 724 (2H

d J=78 Hz) 713 (2H d J=82 Hz) 588 (1H s) 584 (1H s) 566 (1H s) 532 (1H d J=74 Hz) 501

(1H d J=74 Hz) 282ndash264 (2H m) 243 (3H s) 241ndash237 (2H m) 13


20907 16952 14403 14224 14204 13675 13041 (q J=324 Hz) 12965 12753 12715 12586

12367 (q J=2708 Hz) 12227 5894 3434 2835 2147 MS (ESI) mz 458 ([M+Na]+ base peak)

HRMS (ESI) mz calcd for C22H20F3NNaO3S [M+Na]+ 4581008 found 4580999

30h colorless needles mp 46ndash50 ˚C IR (neat) cmndash1

3259 2927 1700 1677 1574 1439 1334 1160

1089 cm-1

1H NMR (400 MHz CDCl3) 764 (2H d J=73 Hz) 727 (2H d J=64 Hz) 719ndash712 (2H

m) 689 (1H d J=69 Hz) 681 (1H s) 588 (1H s) 581 (1H s) 574 (1H s) 519 (1H d J=73)

508ndash506 (1H br m) 282ndash263 (2H m) 245 (3H s) 241ndash228 (2H m) 13


20924 16969 14406 14214 14018 13673 13486 13029 12973 12954 12852 12719 12515

12210 5887 3431 2835 2157 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]

+ base peak) HRMS

(ESI) mz calcd for C21H20ClNNaO3S [M+Na]+ 4240745 found 4240734

30i white needles mp 181ndash183 ˚C IR (KBr) cmndash1

3235 2921 1690 1627 1571 1443 1320 1157 1092

1061 1H NMR (400 MHz CDCl3) 764 (2H d J=83 Hz) 723 (2H d J=78 Hz) 716ndash709 (2H m)

705ndash697 (2H m) 584 (1H s) 581 (1H s) 558 (1H s) 550 (1H d J=68 Hz) 488 (1H br d J=55

Hz) 277ndash273 (2H m) 246ndash231 (5H m) 211 (3H s) 13

C NMR (100 MHz CDCl3) 20943 17053

14368 14268 13730 13602 13575 13119 12955 12893 12835 12708 12642 12166 5563

3440 2841 2151 1875 MS (FAB) mz 404 ([M+Na]+) 382 ([M+H]

+) 154 (base peak) HRMS (FAB)

64

mz calcd for C22H23NNaO3S [M+Na]+ 4041296 found 4041297

Deuteration experiment in Scheme 4-4

54 mg of 27 (005 mmol) and 56 mg of DABCO (005 mmol) or 61 mg of DMAP (005 mmol) were

dissolved in 055 ml of methanol-d4 and stirred at 20

oC After 72 h the solvent was removed in vacuo The

resulting residue was dissolved in CDCl3 and characterized by 1H NMR HMQC and HMBC spectroscopy

Equilibrium experiment in Scheme 4-5

17 mg of 29a (0046 mmol) and 56 mg of DMAP (0046 mmol) were dissolved in 018 mL (025 M) of

CHCl3 and stirred at 20 oC for 24 h no 30a was detected



213 mg of 30a (0058 mmol) and 65 mg of DABCO (0058 mmol) were dissolved in 023 mL (025 M) of

MeOH and stirred at 20 oC for 24 h no 29a was detected

Procedur for Hammett Plot in Scheme 4-6

Relative rates of p-OMe p-Me and p-CF3 substituted N-tosylarylaldimines S28 toward

N-tosylbenzaldimine 28a were evaluated by competition oxidation described below

65

To an equimolar mixture of 28a (259 mg 01 mmol) S28 (01 mmol) and 27 (54 mg 01 mmol) in DMSO

(04 mL 025 M) was added DABCO (112 mg 01 mmol) The resulting mixture was stirred at 20 oC

After the reaction was completed the reaction mixture was poured into 1N HCl aq and extracted with

AcOEt The extracts were dried over Na2SO4 filtered and concentrated The yields of the products and

selectivity were determined by 1H NMR of the residue with 13-dinitrobenzene an an internal standard

Preparation of α-d-27

Iodine (381 mg 003 equiv 015 mmol) was added to a solution of 13-cyclopentanedione (490 mg 50

mmol 10 equiv) in ethanol-d (5 mL) at room temperature and stirred at 35 oC After being stirred at 35

oC

for 96 h the resulting solution was concentrated in vacuo The residual oil was purified by silica gel

column chromatography (AcOEtn-hexane = 11) to afford α-d-3-methoxycyclopent-2-en-1-one as a

colorless oil (460 mg 72 yield) To a solution of α-d-3-methoxycyclopent-2-en-1-one (150 mg 12 mmol

10 equiv) in THF (24 mL) was added dropwise a solution of a vinyl magnesium bromide (1 M in THF

14 mL 12 equiv) at -20 degC under argon Once the addition was complete the resulting solution was

allowed to warm to room temperature and stirred for 30 min The reaction mixture was poured into 1 N

HCl aq at 0 degC The layers were separated and the aqueous layer was extracted with AcOEt (3times50 mL)

The combined organic layers were washed successively with brine dried over Na2SO4 filtered and

concentrated under reduced pressure The crude product was purified by silica gel column chromatography

(AcOEtn-hexane = 3565) to afford α-d-27 as a colorless oil (486 mg 38 yield)

Preparation of α αrsquo γ-d3-27

To a solution of 27 (250 mg 23 mmol) in EtOD (20 mL) was added DMAP (141 mg 12 eq) and stirred

at 40 oC for 63 h To asolution was added DABCO (200 mg) and stirred for 24 h The reaction mixture was

poured into 1 N HCl aq and extracted with AcOEt The extracts were dried over Na2SO4 filtered and

concentrated The crude product was purified by silica gel column chromatography (AcOEtn-hexane =

66

3565) to afford α αrsquo γ-d3-27 as a colorless oil (40 mg 16 yield)

Procedure for determination of kinetic isotope effect in Scheme 4-7

Two stock solutions were prepared in dry 1 mL and 2 mL flasks stock solution A 0234 M in N-tosylimine

28a 0058 M in dibenzylether (internal standard) in DMSO-d6 stock solution B 0070 M in DABCO in

DMSO-d6 Under argon atmosphere to a stirred solution of diene 27 or α-d-27 in 03 mL of DMSO-d

6

were added 03 mL of stock solution A and 01 mL of stock solution B over 30 seconds The resulting

mixture was injected into a NMR tube The sample was periodically submitted to 1H NMR analysis in

order to collect the relative product formation which was taken as the integration of the product divided by

the integration of the standard The relative product formation was plotted versus the time point on

Microsoft Excel The initial kobs was taken as the slope of the linear trendline as calculated by Microsoft

Excel for data points with a ratio of product standard of lt035 The intercept for the linear trendline was

set to zero From these kinetic studies the rate constants for 27 (0169 h-1

) and α-d-27 (0169 h-1

) were

obtained


Two stock solutions were prepared in dry 1 mL and 2 mL flasks stock solution A 020 M in 27 or α

αrsquoγ-d3-27 010 M in dibenzylether (internal standard) in CDCl3 stock solution B 10 M in DMAP in

CDCl3 Under argon atmosphere to N-tosylimine 28a (10 mmol) was added 05 mL of stock solution A

and stirred at 20 oC until imine 28a was dissolved To the resulting reaction mixture was added 01 mL of

stock solution B over 30 seconds The resulting mixture was injected into a NMR tube The sample was

periodically submitted to 1H NMR analysis in order to collect the relative product formation which was

taken as the integration of the product divided by the integration of the standard From these kinetic studies

the rate constants for 27 (00416 h-1

) and α αrsquoγ-d3-27 (0013 h-1

) were obtained

67

68

引用文献

1 Michael A J Prakt Chem 1887 35 349ndash356

2 For reviews see

(a) Alexakis A Baumlckvall J E Krause N Pagravemies O Dieacuteguez M Chem Rev 2008 108 2796ndash2823

(b) Christoffers J Koripelly G Rosiak A Roumlssle M synthesis 2007 1279ndash1300

(c) Alexakis A Benhaim C Eur J Org Chem 2002 3221ndash3236

(d) Zhang Y Wang W Catal Sci Technol 2012 2 42ndash53

3 For selected examples of asymmetric 14-additions of enolates to electron-deficient alkens see

(a) Huang H Jin Z Zhu K Liang X Ye J Angew Chem Int Ed 2011 50 3232ndash3235

(b) Agostinho M Kobayashi S J Am Chem Soc 2008 130 2430ndash2431

(c) Inokuma T Hoashi Y Takemoto Y J Am Chem Soc 2006 128 9413ndash9419

4 (a) Blanco V Leigh D A Lewandowska U Lewandowski B Marcos V J Am Chem Soc 2014

136 15775ndash15780

(b) Brandau S Maerten E Jorgensen K A J Am Chem Soc 2006 128 14986-14991

5 For a review see Wei Y Shi M Chem Rev 2013 113 6659ndash6690

6 Jo S Asymmetric Michael Addition of Lithium Propionate to Alpha Beta-Unsaturated Esters A Study

Towards the Toal Synthesis of Lonomycin A form Proquest Umi Dissertation Publishing

7 (a) Kawabata T Majumdar S Tsubaki K Monguchi D Org Biomol Chem 2005 3 1609ndash1611

(b) Yoshimura T Kinoshita T Yoshioka H Kawabata T Org Lett 2013 15 864ndash867

8 Tomohara K Yoshimura T Hyakutake R Yang P Kawabata T J Am Chem Soc 2013 135

13294ndash13297

9 Yoshimura T Takuwa M Tomohara K Uyama M Hayashi K Yang P Hyakutake R Sasamori

T Tokitoh N Kawabata T Chem Eur J 2012 18 15330ndash15336

10 (a) Seebach D Aebi J D Tetrahedron Lett 1984 25 2545ndash2548

(b) Seebach D Sting A R Hoffmann M Angew Chem Int Ed Engl 1996 35 2708ndash2748

(c) Andrews M D Brewster A G Moloney M G Owen K L J Chem Soc Perkin Trans 1

1996 227ndash228

(d) Andrews M D Brewster A G Moloney M G Synlett 1996 612ndash614

(e) Andrews M D Brewster A G Crapnell K M Ibbett A J Jones T Moloney M G Prout

K Watkin D J Chem Soc Perkin Trans 1 1998 223ndash235

(f) Alezra V Bonin M Chiaroni A Micouin L Riche C Husson H-P Tetrahedron Lett 2000

41 1737ndash1740

(g) Alezra V Bonin M Micouin L Husson H-P Tetrahedron Lett 2001 42 2111ndash2113

(h) Brunner M Koskinen A M P Tetrahedron Lett 2004 45 3063ndash3065

(i) Jimeacutenez-Oseacutes G Aydillo C Busto J H Zurbano M M Peregrina J M Avenoza A J Org

Chem 2007 72 5399ndash5402

11 Moriyama K Sakai H Kawabata T Org Lett 2008 10 3883ndash3886

69

12 Yoshikawa M Yokokawa Y Okuno Y Murakami N Chem Pharm Bull 1994 42 994ndash996

13 Yoshioka S Nagatomo M Inoue M Org Lett 2015 17 90ndash93

14 Burnett D A Caplen M A Davis H R Jr Burrier R E Clarder J W J Med Chem 1994 37

1733ndash1736

15 Aoyama Y Uenaka M Kii M Tanaka M Konoike T Hayasaki-Kajiwara Y Naya N Nakajima

M Bioorg Med Chem 2001 9 3065ndash3075

16 Banik I Becker F F Banik B K J Med Chem 2003 46 12ndash15

17 Palomo C Aizpurua J M Balentovaacute E Jimenez A Oyarbide J Fratila R M Miranda J I Org

Lett 2007 9 101ndash104

18 Alcaide B Almendros P Aragoncillo C Chem Rev 2007 107 4437ndash4492

19 Zhang H M Gao Z H Ye S Org Lett 2014 16 3079ndash3081

20 (a) Kawabata T Kawakami S Majumdar S J Am Chem Soc 2003 125 13012ndash13013

(b) Teraoka F Fuji K Ozturk O Yoshimura T Kawabata T synlett 2011 4 543ndash546

(c) Yoshimura T Kinoshita T Yoshioka H Kawabata T Org Lett 2013 15 864ndash867

21 Panek J S Beresis R Xu F Yang M J Org Chem 1991 56 7341ndash7344

22 (a) Kawabata T Chen J Suzuki H Nagae Y Kinoshita T Chancharunee S Fuji K Org Lett

2000 2 3883ndash3885

(b) Kawabata T Majumdar S Tsubaki K Monguchi D Org Biomol Chem 2005 3 1609ndash1611

23 (a) Houk K N Paddon-Row M N Rondan N G Wu Y-D Brown F K Spellmeyer D C

Metz J T Li Y Loncharich R J Science 1986 231 1108ndash1117

(b) Houk K N Moses S R Wu Y-D Rondan N G Jaumlger V Schohe R Fronczek F R J Am

Chem Soc 1984 106 3880ndash3882

(c) Fujita M Ishida M Manako K Sato K Ogura K Tetrahedron Lett 1993 34 645ndash648

24 For reviews see Declerck V Martinez J Lamaty F Chem Rev 2009 109 1ndash47

25 (a) Back T G Rankic D A Sorbetti J M Wulff J E Org Lett 2005 7 2377ndash2379

(b) Sorbetti J M Clary K N Rankic D A Wulff J E Parvez MBack T G J Org Chem

2007 72 3326ndash3331

(c) Shi Y-L Shi M Tetrahedron 2006 62 461ndash475

(d) Clary K N Back T G synlett 2007 19 2995ndash2998

(e) Duvvuru D Betzer J-F Retailleau P Frison G Marinetti A Adv Synth Catal 2011 353

483ndash493

(f) Schuler M Duvvuru D Ratailleau P Betzer J-F Marinetti A Org Lett 2009 11 4406-4409

26 It was reported that the γ-adduct of an αβγδ-unsaturated lactone was obtained under aza-MBH

conditions with concomitant reduction of the γδ-double bond see Duvvuru D Retailleau P Betzer

J-F Marinetti A Eur J Org Chem 2012 5 897ndash900

27 γ-Selective MBH reactions of αγ-dialkyl-allenoates were reported see Selig P Turočkin A Raven

W synlett 2013 24 2535ndash2539

28 (a) Koumlck M Grube A Seiple I B Baran P S Angew Chem Int Ed 2007 46 6586ndash6594

70

(b) Veits G K Wenz D R Palmer L I St Amant A H Hein J E Alaniz J R Org Biomol

Chem 2015 13 8465ndash8469

29 For selected examples of 14-additions to electron-deficient dienes see

(a) Hayashi Y Okamura D Umemiya S Uchimaru T ChemCatChem 2012 4 959ndash962

(b) Huang H Jin Z Zhu K Liang X Ye J Angew Chem Int Ed 2011 50 3232ndash3235

(c) Shepherd N E Tanabe H Xu Y Matsunaga S Shibasaki M J Am Chem Soc 2010 132

3666ndash3667

(d) Vakulya B Varga S Sooacutes T J Org Chem 2008 73 3475ndash3480

(e) Park S-Y Morimoto H Matsunaga S Shibasaki M Tetrahedron Lett 2007 48 2815ndash2818


(a) Uraguchi D Yoshioka K Ueki Y Ooi T J Am Chem Soc 2012 134 19370ndash19373

(b) Akagawa K Nishi N Sen J Kudo K Org Biomol Chem 2014 12 3581ndash3585

(c) Dellrsquos Amico L Albrecht Ł Naicker T Poulsen P H Joslashrgensen K A J Am Chem Soc

2013 135 8063ndash8070

(d) Tian X Melchiorre P Angew Chem Int Ed 2013 52 5360ndash5363

(e) Tian X Liu Y Melchiorre P Angew Chem Int Ed 2012 51 6439ndash6442

(f) Magrez M Wencel-Delord J Alexakis A Creacutevisy C Mauduit M Org Lett 2012 14

3576ndash3579

31 Bernardi L Loacutepez-Cantarero J Niess B Joslashrgensen K A J Am Chem Soc 2007 129 5772ndash5778

32 (a) Denmark S E Heemstra J R Jr J Org Chem 2007 72 5668ndash5688

(b) Utsumi N Zhang H Tanaka F Barbas C F III Angew Chem Int Ed 2007 46 1878ndash1880

(c) Thebtaranonth Y Yenjai C Tetrahedron Lett 1985 26 4097ndash4100

(d) Vedejs E Gapinski D M Tetrahedron Lett 1981 22 4913ndash4916

(e) Yamaguchi A Aoyama N Matsunaga S Shibasaki M Org Lett 2007 9 3387ndash3390

(f) Saito S Shiozawa M Ito M Yamamoto H J Am Chem Soc 1998 120 813ndash814

(g) Van Maanen H L Kleijn H Jastrzebski J T B H Lakin M T Spek A L van Koten G J

Org Chem 1994 59 7849ndash7848

33 (a) Lindner C Liu Y Karaghiosoff K Maryasin B Zipse H Chem Eur J 2013 19 6429ndash6434

34 Some s values of reactions with para-substituted benzaldehydes are

(a) 12 M Kitamura H Oka R Noyori Tetrahedron 1999 55 3605ndash3614

(b) -065 W K Seok T J Meyer Inorg Chem 2005 44 3931ndash3941

(c) 079 P Fristrup M Kreis A Palmelund P-O Norrby R Madsen J Am Chem Soc 2008 130

5206ndash5215

(d) 085 H Yamataka M Shimizu M Mishima Bull Chem Soc Jpn 2002 75 127ndash129

(e) 135 M Shibagaki H Kuno K Takahashi H Matsushita Bull Chem Soc Jpn 1988 61 4153

ndash5154

(f) 066-104 T Kudo T Higashide S Ikedate H Yamataka J Org Chem 2005 70 5157ndash5163

(g) 124 N Kurono M Yamaguchi K Suzuki T Ohkuma J Org Chem 2005 70 6530ndash6532

71

(h) 091 L Koren-Selfridge H N Londino J K Vellucci B J Simmons C P Casey T B Clark

Organometallics 2009 28 2085ndash2090

35 Saunders L B Cowen B J Miller S J Org Lett 2010 12 4800ndash4803

36 Buskens P Klankermayer J Leitner W J Am Chem Soc 2005 127 16762ndash16763

37 (a) Bhosale R S Bhosale S V Bhosale S V Wang T Zubaidha P K Tetrahedron Lett 2004 45

7187ndash7188

(b) Fisher M J Hehre W J Kahn S D Overman L E J Am Chem Soc 1988 110 4625ndash4633

38 Love B E Raje P S Williams T C II Synlett 1994 7 493ndash494

72

73

謝辞

本論文の終わりに臨み本研究を行うに際し終始ご指導ご鞭撻を賜りました京都大学化学研究

所川端猛夫教授に感謝の意を表します哲学を持って研究する事の大切さを教えて頂きま

したまた学生の考えた研究案を客観的な立場で親身に聞いて議論してくださりその研究を

遂行する機会をいただきました川端研の哲学に基づいて自由に研究を行えた経験は何物にも代

えがたい貴重な体験であり心より感謝申し上げます

本研究を行うに当たりX 線結晶構造解析の取得並びに有益なご助言を賜りました京都大学化

学研究所古田巧准教授に深く感謝申し上げます古田先生とのディスカッションを通じ

研究に対する多様な視点のあて方を勉強させていただきました

本研究の遂行に当たり直接ご指導を賜りました金沢大学吉村智之准教授に厚く御礼申

し上げます有機合成化学の実験操作や研究の進め方研究室生活における心掛け等を学部 4回

生の時から教えていただき自分の研究に関する基礎の大部分を築いていただきました

日々の研究方針に関する議論や論文作成の御指導を頂きました京都大学化学研究所上田善

弘助教に心より感謝の意を表します上田先生は著者が学部四回生の時の博士課程一回生の先

輩にあたり博士課程の学生像を築いてくださいました

また本論文をご精読賜りました京都大学薬学研究科竹本佳司教授ならびに京都大学

薬学研究科高須清誠教授に深謝致します

本研究に関しましてX 線結晶構造の取得にご協力を賜りました京都大学化学研究所時任

宣博教授ならびに笹森貴裕准教授に深く感謝致します

研究室の引っ越しに伴い約半年間実験環境をご提供くださいました京都大学化学研究所二

木史朗教授および京都大学化学研究所生体機能設計化学領域の皆様に感謝申し上げます

本研究におきまして質量分析を行って頂きました藤橋明子氏犬塚真弓氏なら

びに元素分析を行って頂きました平野敏子氏に深く感謝いたします

第三章の実験におきましてL-allo-スレオニンを快くご提供くださいました渡辺化学工業の皆

様に深く感謝申し上げます

本研究に関しまして多大なるご協力ご助言を頂きました精密有機合成化学分野卒業生友

原啓介博士 (現富山大学付属病院助教)吉岡広泰修士木下智彦博士楊畔

博士に厚く御礼申し上げます

本研究におきまして関連するテーマに取り組んだ共同研究者としてご協力を賜りました笠

松幸司修士大津寄悠修士権藤匠洋学士に深く感謝致します

有意義な学生生活を共に送ることが出来た京都大学化学研究所精密有機合成化学分野の卒業生

ならびに在学生の皆様に感謝致します特に博士後期課程の同期の学生として切磋琢磨し合え

た竹内裕紀氏津田(今吉) 亜由美氏平田篤志氏陸文傑氏および同時期に

卒業する馬場智明氏柳正致氏に深く感謝致しますまた研究生活を事務方として

支援してくださった京都大学化学研究所橋本香織氏に御礼申し上げます

最後に九年間に及ぶ学生生活において終始経済的精神的に支えていただきました両親に

心から感謝致します

不飽和カルボニル化合物への共役付加を基盤とする

選択的反応の開発

2015

百武龍一

1


目次

理論の部

第一章序論 5










立体化学 16










第五章結論 33

実験の部




2


謝辞 73

3

理論の部

4

5

第一章緒言





















斉合成



6













た (eq 2)













7




























8




















9














10

























11












12












た









13









となった














14














15

16

















17












18

















19









20



















21







22

23























24


























25










26









27














28












29





成に優先した





30



















31









はσC-N+











32


33

第五章結論







合成























34

















35

実験の部

36

37
















38


21 Chapter 2

Synthesis of 4














yellow oil




099H) 146 (s 801H) 123 (t 73 Hz 267H) 116 (t 73 Hz 033H) 13


16847 16833 16697 16579 16451 15895 15860 13758 13719 13415 13398 13273 13256

12927 12903 12847 12820 (2 peaks) 12802 12765 12751 12744 12737 11388 11343 8136

7304 6827 6689 6168 6116 6021 5918 5510 5156 2780 1395 1376 MS (FAB) mz 498

(M+H)+ 520 (M+Na)


+ found

4982491


39










136ndash131 (6H m)










colorless oil []D18




Hz 1H) 216 (s 1H) 125 (t 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17308 15864 13786 13173

12947 12827 12756 12750 11368 7310 7106 6080 6031 5518 5133 1422 IR (neat) cmndash1

2934 2906 2864 1736 1611 1513 1458 1368 1300 1248 1185 1102 1034 MS (FAB) mz 344

(M+H) +

366 (M+Na) +


3441862 found

3441860

40




Hz 3H) 102 (s 9H) 13

C-NMR (100 MHz CDCl3) 17339 15859 13555 13552 13308 13189

12998 12933 12764 11368 6517 6193 6071 5520 5115 2666 1919 1425 IR (neat) cmndash1

MS

(FAB) mz 492 (M+H) +


4922570 found

4922570


= -52 (c 1087 CHCl3) 1H-NMR (400 MHz






Hz 51100 H) 13

C-NMR (100 MHz CDCl3) 1684 1649 1644 1628 1591 1377 1358 1334 1292

1285 1284 1283 1282 1278 1276 1275 1140 1135 732 685 621 618 613 586 552 519 140


2983 2937 1741 1655 1514 1449 1370 1251 1207 1069 1029 MS (FAB) mz

542 (M+H) +

564 (M+Na) +


5422390 found

5422394


= -40 (c 0750 CHCl3) 1H-NMR (400



(9H m) 13

C-NMR (100 MHzCDCl3) 16830 16486 16440 16275 15921 13586 13336 12934

12846 12805 11404 11357 9957 6602 6214 6186 6140 5843 5551 5533 5527 5184 1400


2983 2938 2841 1742 1655 1514 1463 1372 1253 1211 1113 1068

1039 IR (neat) cm-1

2983 2938 1742 1655 1514 1463 1372 1253 1211 1113 1068 1039 MS (FAB)

mz 496 (M+H) +


+ 4962183

found 4962182

41


= -47 (c 0597 CHCl3) 1H-NMR (400




(t J = 75 Hz 06H) 13

C-NMR (100 MHz CDCl3) 16849 16478 16449 16280 15911 13590

13559 13550 13296 13271 13264 12984 12979 12921 12831 12773 12770 11409 11385

11356 6255 6211 6176 6128 6007 5526 5159 2676 1907 1394 1388 IR (neat) cmndash1

2958

2933 2857 1739 1656 1514 1466 1426 1370 1252 1205 1178 1111 1069 1030 MS (FAB) mz 690

(M+H)+712 (M+Na)


+ 6903098 found

6903095
















64 Hz 1H) 284 (m 2H) 131ndash128 (m 12H) 13

C-NMR (100 MHz CDCl3) 17365 15879 13165

42

12958 11381 6101 6037 5531 5135 4233 3158 3094 1442 IR (neat) cmndash1

2962 2902 2836

1734 1612 1513 1462 1367 1300 1247 1178 1034 MS (FAB) mz 326 (M+H) +

348 (M+Na)+ 121 (base


3261790 found 3261786















20100 H) 136ndash108 (m 18 H) 13

C-NMR (100 MHz CDCl3) 16896 16881 16567 16548 16430 16426

16277 15941 15888 13613 13568 13426 13367 12964 12925 12879 12717 11399 11359 6215

6195 6186 6148 5987 5527 5266 4299 4285 3076 3065 2798 2764 1399 1391 1380 IR (neat)

cmndash1

2966 2904 2839 1734 1653 1514 1462 1369 1303 1253 1212 1069 1031 MS (FAB) mz 524

(M+H) +

546 (M+Na) +


5242318 found

5242313









λ = 254 nm t=169 min t=232 min []D18


43




C-NMR

(100 MHz CDCl3) 16952 16947 16715 15882 13745 12993 12881 12829 12764 12741

11359 8131 7316 710 6719 6169 5522 5165 4505 3129 2793 1412 IR (neat) cmndash1

2979

2932 2867 1764 1735 1612 1514 1455 1392 1368 1247 1154 1032 MS (FAB) mz 498 (M+H) +

520

(M+Na) +


4982492 found 4982491


t=165 min t=191 min []D18




1H) 271 (d J 78 Hz 2H) 139 (s 3H) 119 (t J 74 Hz 3H) 13


16988 16774 15891 13718 13003 12837 12824 12778 12760 11363 8129 7337 6797 6447

6162 5523 5354 4480 3090 2788 1298 IR (neat) cmndash1

2979 2931 2869 1765 1732 1612 1514

1456 1391 1367 1248 1154 1097 1063 1031 MS (FAB) mz 498 (M+H) +

520 (M+Na) +

121 (base


4982492 found 4982491







2983 2913 2845 1767 1735 1611 1588 1514 1453 1388 1247 1177 1105

1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +


(M+H) +

4362335 found 4362335





2H) 143 (s 9H) 120 (t J 73 Hz 3H) 110 (t J 69 Hz 3H) 13


17003 16786 15895 13006 12829 11360 8126 6803 6678 6443 6156 5528 5350 4478

3092 2795 1489 1400 IR (neat) cmndash1

2976 2931 2873 1762 1734 1613 1514 1461 1390 1369

1292 1244 1152 1113 1064 1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +



4362335 found 4362335

44















086 (t J = 69 Hz 3H) 081 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1696 1672 1668

1649 1594 1381 1303 1294 1285 1283 1278 1277 1139 733 711 667 623 619 616 548

547 501 453 1394 138 2 1382 IR (neat) cmndash1

2983 2935 2869 1766 1739 1612 1514 1456

1392 1369 1301 1249 1176 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +



5422390 found 5422400






J = 73 Hz 3H) 078 (t J = 73 Hz 3H) 070 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1699 1677

1671 1657 1595 1376 1305 1286 1286 1283 12804 12800 1140 7344 6705 6415 6214 6178

6152 5673 5471 4943 4461 1397 1380 1370 IR (neat) cmndash1

2983 2935 2871 1769 1735 1612 1514

1458 1391 1369 1301 1249 1178 1098 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +

121 (base peak)


5422390 found 5422393

45



= -16 (c 0719 CHCl3 96 ee) 1H-NMR (400 MHz




C-NMR (100

MHz CDCl3) 1692 1667 1666 1656 1589 1358 1357 1324 1300 1299 1278 1277 1137

668 633 621 620 617 552 529 492 449 268 192 1394 1380 137 IR (neat) cmndash1

2961

2934 2859 2369 2315 1769 1736 1650 1613 1514 1468 1428 1390 1370 1301 1251 1177 1108

1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


C38H48NO9Si (M+H) +

6903098 found 6903098







(s 9H) 099 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1695 1676 1670 1660 1589 1362

1357 1323 1318 1303 1300 1280 1278 1267 1136 639 6206 6202 614 597 552 483

441 269 190 1396 1392 136 IR (neat) cmndash1

2961 2934 2859 2369 2315 1769 1736 1650 1613

1514 1468 1428 1390 1370 1301 1251 1177 1108 1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


6903098 found 6903098


46












124 (t J = 68 Hz 3H) 114 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1697 1671 1666

1591 1304 1274 1137 655 622 6203 6196 555 553 493 453 427 320 307 139 138 IR

(neat) cmndash1

2966 2937 2868 1770 1734 1613 1514 1464 1389 1368 1301 1248 1178 1095 1033

MS (FAB) mz 524 (M+H) +

546 (M+Na) +


(M+H) +

5242318 found 5242318



= 24 (c 0551 CHCl3 91 ee) 1H-NMR (400 MHz




C-NMR (100 MHz

CDCl3) 1699 1672 1666 1654 1591 1303 1276 1137 643 6219 6219 6212 6198 560

553 485 453 428 303 291 140 138 IR (neat) cmndash1

2969 1769 1738 1613 1514 1464 1389

1369 1301 1248 1178 1034 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


mz 524 (M+H) +

546 (M+Na) +


5242318 found 5242313












47




















13659 13031 12849 12833 12805 12760 12157 12144 11379 8783 8749 7347 6855 6695 5522










b = 120516(8) Aring = 90deg

c = 271658(19) Aring = 90deg


48

Z 4



F(000) 1608















49

22 Chepter 3














122 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17340 15856 13834 13206 12945 12821

12758 12747 11357 7557 7075 6468 6064 5518 5170 1635 1421 IR (neat) cmndash1

2979 2932

2838 1734 1612 1512 1459 1373 1299 1247 1184 1159 1094 1032 MS (FAB) mz 358 (M+H) +

380 (M+Na) +


3582018 found

3582010














(m 356H) 133ndash118 (m 1115H) 111 (t J = 76 Hz 084 H) 13


50

16816 16636 16551 16455 16405 16302 16273 15888 15856 13824 13766 13612 13528

13398 13306 13096 12955 12945 12878 12832 12827 12809 12767 12757 12751 12726

12660 11377 11329 7416 7161 7135 7080 6563 6221 6195 6167 6118 5517 7167 1732

1663 1393 1385 1370 IR (neat) cmndash1

2981 2936 2905 1738 1652 1513 1457 1372 1250 1205

1177 1096 1067 1030 MS (FAB) mz 556 (M+H)+ 578 (M+Na)



5562547 found 5562547























51







13C-NMR (100 MHz CDCl3) 17382 15864 13832 13180 12947 12821 12747 11365 7634

7091 6465 6065 5522 5147 1657 1431 IR (neat) cmndash1

2979 2933 2837 1730 1611 1513 1460

1372 1302 1247 1185 1108 1033 MS (FAB) mz 358 (M+H) +

380 (M+Na) +



3582018 found 3582023









a colorless oil



oC) 737ndash720 (m


131ndash115 (m 12H) 13

C-NMR (100 MHz CDCl3) 16879 16872 16586 16491 16444 16396

16272 15920 15885 13827 13754 13584 13551 13513 13355 12972 12894 12852 12837

12824 12798 12787 12778 12749 11403 11355 7490 7341 7219 7117 6505 6219 6214

6185 6151 6112 5525 5520 5151 1641 1619 1397 1386 IR (neat) cmndash1

2982 2937 2905

1739 1656 1613 1513 1450 1373 1252 1203 1095 1070 1030 MS (FAB) mz 556 (M+H) +

578


+ found 5562549





52








094 (t J = 74 Hz 3H) 085 (t J = 74 Hz 3H) 13

C-NMR (100 MHz C6D6) 1702 1677 1673 1663

1598 1395 1308 1303 1290 1289 1281 1279 1145 784 716 713 628 625 621 5529

5526 513 465 161 1454 1450 1445 IR (neat) cmndash1

2981 2925 1766 1739 1648 1612 1514

1461 1390 1371 1301 1249 1178 1096 1031 MS (FAB) mz 556 (M+H) +



5562547 found 5562545







C-NMR (100

MHz C6D6) 1707 1671 1667 1651 1593 1387 1312 1300 1285 1283 1277 1276 1138 766

719 716 624 619 616 546 542 505 466 140 139 124 IR (neat) cmndash1

2983 2938 1766 1739

1613 1514 1459 1373 1248 1177 1148 1097 1032 MS (FAB) mz 556 (M+H) +

121 (base peak)


5562547 found 5562549




C-NMR (100

MHz CDCl3) 17035 16717 16663 16632 15871 13750 12961 12854 12832 12772 12766

11357 7216 7007 6893 6202 6187 5606 5520 4872 4588 1547 1403 1399 1396 IR (neat)

cmndash1

2983 2914 2845 1767 1735 1611 1588 1514 1453 1388 1248 1177 1105 1032 MS (FAB)

mz 556 (M+H) +


5562547 found

5562546



53





















54











3033 2359 2306

1737 1677 1610 1585 1537 1516 1486 1394 1322 1248 1179 1117 1061 1033 1006 MS (FAB) mz

1095 (M+Na) +


10949589 found

10949577







Space group C2221


b = 30665(2) Aring = 90deg

c = 134874(12) Aring = 90deg


Z 8



F(000) 4544











55











Space group C2(5)


b = 75202(3) Aring = 1025865(14)deg

c = 236650(9) Aring = 90deg


Z 8



F(000) 2368















56

23 Chapter 4















3560 3092 3010 2924 1706 1673 1627 1573 1440 1410 1346 1290












57






1H




3298 3058 2958 1678 1629 1581 1448 1419 1358




194ndash187 (1H m) 13

C NMR (100 MHz CDCl3) 20910 16553 14294 13841 13754 13634

12973 12914 12858 12767 12711 12640 12437 5337 3368 2522 2142 MS (ESI) mz 390


+ 3901134 found 3901138










3265 3028 2924 1676 1573 1494 1449 1330 1190 1159 1088 1H



245ndash228 (5H m) 13

C NMR (100 MHz CDCl3) 20938 17011 14378 14253 13821 13688 12966

12943 12908 12843 12727 12699 12155 5944 3429 2837 2156 MS (ESI) mz 390 ([M+Na]+)

58






29




30 respectively


3276 1684 1631 1599 1518 1432 1348 1162 1089




(2H m) 205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20885 16645 14728 14557 14346

13728 13533 12935 12922 12736 12703 12552 12378 5275 3364 2545 2144 MS (FAB) mz

435 ([M+Na]+) 413 ([M+H]


+

4350991 found 4350991


3276 2928 1683 1631 1584 1511 1432 1335 1307 1249 1165 1092



59


(1H m) 13

C NMR (100 MHz CDCl3) 20919 16528 15904 14286 13759 13653 13058 12975

12912 12769 12714 12422 11392 5523 5299 3372 2519 2141 MS (FAB) mz 420 ([M+Na]+)



3269 2922 1684 1630 1583 1491 1426 1338 1162 1091 1H NMR





16579 14313 13747 13695 13600 13362 12952 12922 12872 12785 12709 12477 5285

3370 2529 2144 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3272 2921 1684 1630 1428 1338 1162 1092 1H NMR (400 MHz




(1H m) 13

C NMR (100 MHz CDCl3) 20913 16534 14287 13759 13747 13651 13548 12978

12926 12912 12714 12633 12421 5321 3370 2520 2142 2098 MS (ESI) mz 404 ([M+Na]+



3273 2922 1685 1630 1585 1488 1426 1338 1071 1011 1H NMR



60


m) 13

C NMR (100 MHz CDCl3) 20906 16581 14315 13748 13745 13593 13166 12951

12923 12818 12708 12481 12176 5292 3370 2529 2145 MS (FAB) mz 470 ([M+2+Na]+ base


[M+Na]+ 4680245 found 4682045


3271 2923 1687 1630 1585 1425 1328 1163 1121 1068 1018 1H




205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20904 16607 14322 14234 13740 13574

12986 (q J=324 Hz) 12939 12924 12703 12683 12552 (q J=27 Hz) 12506 12385 (q J=2708

Hz) 5310 3368 2535 2137 MS (FAB) mz 458 ([M+Na]+) 436 ([M+H]




3267 1685 1631 1594 1434 1339 1162 1092 1H NMR (400 MHz




C NMR (100 MHz CDCl3) 20900 16598

14315 14039 13741 13579 13450 12985 12948 12923 12788 12705 12660 12489 12462

5290 3368 2532 2143 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3261 1692 1630 1581 1491 1427 1342 1321 1162

61




m) 13

C NMR (100 MHz CDCl3) 20965 16573 14293 13732 13644 13635 13629 13093

13990 12901 12811 12740 12734 12617 12420 5106 3372 2528 2144 1981 MS (FAB) mz

404 ([M+Na]+) 382 ([M+H]


+)

4041296 found 4041296


3265 2925 1698 1677 1575 1522 1442 1346



m) 244 (3H s) 241ndash237 (2H m) 13

C NMR (100 MHz CDCl3) 20879 16906 14755 14539

14435 14204 13663 12977 12970 12805 12716 12403 12280 5878 3433 2834 2156 MS


+ 4350985

found 4350980


3263 2925 1702 1676 1611 1574 1512 1442 1329 1253 1159 1088




C NMR (100 MHz CDCl3) 20939 17019

15960 14381 14266 13687 13026 12972 12942 12828 12731 12116 11446 5895 5527


[M+Na]+ 4201240 found 4201233

62


3262 2923 1677 1575 1491 1441 1333 1160

1090 cm-1





20924 16980 14391 14234 13684 13672 13423 12966 12951 12910 12845 12716 12285

5874 3429 2835 2155 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3265 2924 1698 1677 1574 1442 1332 1188 1160 1089 1043 1H





17021 14375 14261 13839 13688 13528 12976 12966 12940 12729 12689 12128 5922




3262 3022 2871 1698 1677 1575 1488 1441 1404 1333 1160




C NMR (100 MHz CDCl3) 20914 16969

14398 14229 13723 13680 13211 12970 12955 12875 12719 12244 12187 5884 3429




63


3261 2927 1698 1677 1620 1575 1442 1327 1161





20907 16952 14403 14224 14204 13675 13041 (q J=324 Hz) 12965 12753 12715 12586




3259 2927 1700 1677 1574 1439 1334 1160

1089 cm-1





20924 16969 14406 14214 14018 13673 13486 13029 12973 12954 12852 12719 12515

12210 5887 3431 2835 2157 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]

+ base peak) HRMS



3235 2921 1690 1627 1571 1443 1320 1157 1092




C NMR (100 MHz CDCl3) 20943 17053

14368 14268 13730 13602 13575 13119 12955 12893 12835 12708 12642 12166 5563

3440 2841 2151 1875 MS (FAB) mz 404 ([M+Na]+) 382 ([M+H]


64

















65









oC
















66






6








) and α-d-27 (0169 h-1

) were

obtained











) were obtained

67

68

引用文献


2 For reviews see










136 15775ndash15780








13294ndash13297






1996 227ndash228





41 1737ndash1740




Chem 2007 72 5399ndash5402


69




1733ndash1736





Lett 2007 9 101ndash104








2000 2 3883ndash3885





Chem Soc 1984 106 3880ndash3882





2007 72 3326ndash3331




483ndash493








70


Chem 2015 13 8465ndash8469





3666ndash3667







2013 135 8063ndash8070




3576ndash3579















5206ndash5215



ndash5154



71






7187ndash7188



72

73

謝辞





































1


目次

理論の部

第一章序論 5










立体化学 16










第五章結論 33

実験の部




2


謝辞 73

3

理論の部

4

5

第一章緒言





















斉合成



6













た (eq 2)













7




























8




















9














10

























11












12












た









13









となった














14














15

16

















17












18

















19









20



















21







22

23























24


























25










26









27














28












29





成に優先した





30



















31









はσC-N+











32


33

第五章結論







合成























34

















35

実験の部

36

37
















38


21 Chapter 2

Synthesis of 4














yellow oil




099H) 146 (s 801H) 123 (t 73 Hz 267H) 116 (t 73 Hz 033H) 13


16847 16833 16697 16579 16451 15895 15860 13758 13719 13415 13398 13273 13256

12927 12903 12847 12820 (2 peaks) 12802 12765 12751 12744 12737 11388 11343 8136

7304 6827 6689 6168 6116 6021 5918 5510 5156 2780 1395 1376 MS (FAB) mz 498

(M+H)+ 520 (M+Na)


+ found

4982491


39










136ndash131 (6H m)










colorless oil []D18




Hz 1H) 216 (s 1H) 125 (t 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17308 15864 13786 13173

12947 12827 12756 12750 11368 7310 7106 6080 6031 5518 5133 1422 IR (neat) cmndash1

2934 2906 2864 1736 1611 1513 1458 1368 1300 1248 1185 1102 1034 MS (FAB) mz 344

(M+H) +

366 (M+Na) +


3441862 found

3441860

40




Hz 3H) 102 (s 9H) 13

C-NMR (100 MHz CDCl3) 17339 15859 13555 13552 13308 13189

12998 12933 12764 11368 6517 6193 6071 5520 5115 2666 1919 1425 IR (neat) cmndash1

MS

(FAB) mz 492 (M+H) +


4922570 found

4922570


= -52 (c 1087 CHCl3) 1H-NMR (400 MHz






Hz 51100 H) 13

C-NMR (100 MHz CDCl3) 1684 1649 1644 1628 1591 1377 1358 1334 1292

1285 1284 1283 1282 1278 1276 1275 1140 1135 732 685 621 618 613 586 552 519 140


2983 2937 1741 1655 1514 1449 1370 1251 1207 1069 1029 MS (FAB) mz

542 (M+H) +

564 (M+Na) +


5422390 found

5422394


= -40 (c 0750 CHCl3) 1H-NMR (400



(9H m) 13

C-NMR (100 MHzCDCl3) 16830 16486 16440 16275 15921 13586 13336 12934

12846 12805 11404 11357 9957 6602 6214 6186 6140 5843 5551 5533 5527 5184 1400


2983 2938 2841 1742 1655 1514 1463 1372 1253 1211 1113 1068

1039 IR (neat) cm-1

2983 2938 1742 1655 1514 1463 1372 1253 1211 1113 1068 1039 MS (FAB)

mz 496 (M+H) +


+ 4962183

found 4962182

41


= -47 (c 0597 CHCl3) 1H-NMR (400




(t J = 75 Hz 06H) 13

C-NMR (100 MHz CDCl3) 16849 16478 16449 16280 15911 13590

13559 13550 13296 13271 13264 12984 12979 12921 12831 12773 12770 11409 11385

11356 6255 6211 6176 6128 6007 5526 5159 2676 1907 1394 1388 IR (neat) cmndash1

2958

2933 2857 1739 1656 1514 1466 1426 1370 1252 1205 1178 1111 1069 1030 MS (FAB) mz 690

(M+H)+712 (M+Na)


+ 6903098 found

6903095
















64 Hz 1H) 284 (m 2H) 131ndash128 (m 12H) 13

C-NMR (100 MHz CDCl3) 17365 15879 13165

42

12958 11381 6101 6037 5531 5135 4233 3158 3094 1442 IR (neat) cmndash1

2962 2902 2836

1734 1612 1513 1462 1367 1300 1247 1178 1034 MS (FAB) mz 326 (M+H) +

348 (M+Na)+ 121 (base


3261790 found 3261786















20100 H) 136ndash108 (m 18 H) 13

C-NMR (100 MHz CDCl3) 16896 16881 16567 16548 16430 16426

16277 15941 15888 13613 13568 13426 13367 12964 12925 12879 12717 11399 11359 6215

6195 6186 6148 5987 5527 5266 4299 4285 3076 3065 2798 2764 1399 1391 1380 IR (neat)

cmndash1

2966 2904 2839 1734 1653 1514 1462 1369 1303 1253 1212 1069 1031 MS (FAB) mz 524

(M+H) +

546 (M+Na) +


5242318 found

5242313









λ = 254 nm t=169 min t=232 min []D18


43




C-NMR

(100 MHz CDCl3) 16952 16947 16715 15882 13745 12993 12881 12829 12764 12741

11359 8131 7316 710 6719 6169 5522 5165 4505 3129 2793 1412 IR (neat) cmndash1

2979

2932 2867 1764 1735 1612 1514 1455 1392 1368 1247 1154 1032 MS (FAB) mz 498 (M+H) +

520

(M+Na) +


4982492 found 4982491


t=165 min t=191 min []D18




1H) 271 (d J 78 Hz 2H) 139 (s 3H) 119 (t J 74 Hz 3H) 13


16988 16774 15891 13718 13003 12837 12824 12778 12760 11363 8129 7337 6797 6447

6162 5523 5354 4480 3090 2788 1298 IR (neat) cmndash1

2979 2931 2869 1765 1732 1612 1514

1456 1391 1367 1248 1154 1097 1063 1031 MS (FAB) mz 498 (M+H) +

520 (M+Na) +

121 (base


4982492 found 4982491







2983 2913 2845 1767 1735 1611 1588 1514 1453 1388 1247 1177 1105

1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +


(M+H) +

4362335 found 4362335





2H) 143 (s 9H) 120 (t J 73 Hz 3H) 110 (t J 69 Hz 3H) 13


17003 16786 15895 13006 12829 11360 8126 6803 6678 6443 6156 5528 5350 4478

3092 2795 1489 1400 IR (neat) cmndash1

2976 2931 2873 1762 1734 1613 1514 1461 1390 1369

1292 1244 1152 1113 1064 1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +



4362335 found 4362335

44















086 (t J = 69 Hz 3H) 081 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1696 1672 1668

1649 1594 1381 1303 1294 1285 1283 1278 1277 1139 733 711 667 623 619 616 548

547 501 453 1394 138 2 1382 IR (neat) cmndash1

2983 2935 2869 1766 1739 1612 1514 1456

1392 1369 1301 1249 1176 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +



5422390 found 5422400






J = 73 Hz 3H) 078 (t J = 73 Hz 3H) 070 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1699 1677

1671 1657 1595 1376 1305 1286 1286 1283 12804 12800 1140 7344 6705 6415 6214 6178

6152 5673 5471 4943 4461 1397 1380 1370 IR (neat) cmndash1

2983 2935 2871 1769 1735 1612 1514

1458 1391 1369 1301 1249 1178 1098 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +

121 (base peak)


5422390 found 5422393

45



= -16 (c 0719 CHCl3 96 ee) 1H-NMR (400 MHz




C-NMR (100

MHz CDCl3) 1692 1667 1666 1656 1589 1358 1357 1324 1300 1299 1278 1277 1137

668 633 621 620 617 552 529 492 449 268 192 1394 1380 137 IR (neat) cmndash1

2961

2934 2859 2369 2315 1769 1736 1650 1613 1514 1468 1428 1390 1370 1301 1251 1177 1108

1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


C38H48NO9Si (M+H) +

6903098 found 6903098







(s 9H) 099 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1695 1676 1670 1660 1589 1362

1357 1323 1318 1303 1300 1280 1278 1267 1136 639 6206 6202 614 597 552 483

441 269 190 1396 1392 136 IR (neat) cmndash1

2961 2934 2859 2369 2315 1769 1736 1650 1613

1514 1468 1428 1390 1370 1301 1251 1177 1108 1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


6903098 found 6903098


46












124 (t J = 68 Hz 3H) 114 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1697 1671 1666

1591 1304 1274 1137 655 622 6203 6196 555 553 493 453 427 320 307 139 138 IR

(neat) cmndash1

2966 2937 2868 1770 1734 1613 1514 1464 1389 1368 1301 1248 1178 1095 1033

MS (FAB) mz 524 (M+H) +

546 (M+Na) +


(M+H) +

5242318 found 5242318



= 24 (c 0551 CHCl3 91 ee) 1H-NMR (400 MHz




C-NMR (100 MHz

CDCl3) 1699 1672 1666 1654 1591 1303 1276 1137 643 6219 6219 6212 6198 560

553 485 453 428 303 291 140 138 IR (neat) cmndash1

2969 1769 1738 1613 1514 1464 1389

1369 1301 1248 1178 1034 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


mz 524 (M+H) +

546 (M+Na) +


5242318 found 5242313












47




















13659 13031 12849 12833 12805 12760 12157 12144 11379 8783 8749 7347 6855 6695 5522










b = 120516(8) Aring = 90deg

c = 271658(19) Aring = 90deg


48

Z 4



F(000) 1608















49

22 Chepter 3














122 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17340 15856 13834 13206 12945 12821

12758 12747 11357 7557 7075 6468 6064 5518 5170 1635 1421 IR (neat) cmndash1

2979 2932

2838 1734 1612 1512 1459 1373 1299 1247 1184 1159 1094 1032 MS (FAB) mz 358 (M+H) +

380 (M+Na) +


3582018 found

3582010














(m 356H) 133ndash118 (m 1115H) 111 (t J = 76 Hz 084 H) 13


50

16816 16636 16551 16455 16405 16302 16273 15888 15856 13824 13766 13612 13528

13398 13306 13096 12955 12945 12878 12832 12827 12809 12767 12757 12751 12726

12660 11377 11329 7416 7161 7135 7080 6563 6221 6195 6167 6118 5517 7167 1732

1663 1393 1385 1370 IR (neat) cmndash1

2981 2936 2905 1738 1652 1513 1457 1372 1250 1205

1177 1096 1067 1030 MS (FAB) mz 556 (M+H)+ 578 (M+Na)



5562547 found 5562547























51







13C-NMR (100 MHz CDCl3) 17382 15864 13832 13180 12947 12821 12747 11365 7634

7091 6465 6065 5522 5147 1657 1431 IR (neat) cmndash1

2979 2933 2837 1730 1611 1513 1460

1372 1302 1247 1185 1108 1033 MS (FAB) mz 358 (M+H) +

380 (M+Na) +



3582018 found 3582023









a colorless oil



oC) 737ndash720 (m


131ndash115 (m 12H) 13

C-NMR (100 MHz CDCl3) 16879 16872 16586 16491 16444 16396

16272 15920 15885 13827 13754 13584 13551 13513 13355 12972 12894 12852 12837

12824 12798 12787 12778 12749 11403 11355 7490 7341 7219 7117 6505 6219 6214

6185 6151 6112 5525 5520 5151 1641 1619 1397 1386 IR (neat) cmndash1

2982 2937 2905

1739 1656 1613 1513 1450 1373 1252 1203 1095 1070 1030 MS (FAB) mz 556 (M+H) +

578


+ found 5562549





52








094 (t J = 74 Hz 3H) 085 (t J = 74 Hz 3H) 13

C-NMR (100 MHz C6D6) 1702 1677 1673 1663

1598 1395 1308 1303 1290 1289 1281 1279 1145 784 716 713 628 625 621 5529

5526 513 465 161 1454 1450 1445 IR (neat) cmndash1

2981 2925 1766 1739 1648 1612 1514

1461 1390 1371 1301 1249 1178 1096 1031 MS (FAB) mz 556 (M+H) +



5562547 found 5562545







C-NMR (100

MHz C6D6) 1707 1671 1667 1651 1593 1387 1312 1300 1285 1283 1277 1276 1138 766

719 716 624 619 616 546 542 505 466 140 139 124 IR (neat) cmndash1

2983 2938 1766 1739

1613 1514 1459 1373 1248 1177 1148 1097 1032 MS (FAB) mz 556 (M+H) +

121 (base peak)


5562547 found 5562549




C-NMR (100

MHz CDCl3) 17035 16717 16663 16632 15871 13750 12961 12854 12832 12772 12766

11357 7216 7007 6893 6202 6187 5606 5520 4872 4588 1547 1403 1399 1396 IR (neat)

cmndash1

2983 2914 2845 1767 1735 1611 1588 1514 1453 1388 1248 1177 1105 1032 MS (FAB)

mz 556 (M+H) +


5562547 found

5562546



53





















54











3033 2359 2306

1737 1677 1610 1585 1537 1516 1486 1394 1322 1248 1179 1117 1061 1033 1006 MS (FAB) mz

1095 (M+Na) +


10949589 found

10949577







Space group C2221


b = 30665(2) Aring = 90deg

c = 134874(12) Aring = 90deg


Z 8



F(000) 4544











55











Space group C2(5)


b = 75202(3) Aring = 1025865(14)deg

c = 236650(9) Aring = 90deg


Z 8



F(000) 2368















56

23 Chapter 4















3560 3092 3010 2924 1706 1673 1627 1573 1440 1410 1346 1290












57






1H




3298 3058 2958 1678 1629 1581 1448 1419 1358




194ndash187 (1H m) 13

C NMR (100 MHz CDCl3) 20910 16553 14294 13841 13754 13634

12973 12914 12858 12767 12711 12640 12437 5337 3368 2522 2142 MS (ESI) mz 390


+ 3901134 found 3901138










3265 3028 2924 1676 1573 1494 1449 1330 1190 1159 1088 1H



245ndash228 (5H m) 13

C NMR (100 MHz CDCl3) 20938 17011 14378 14253 13821 13688 12966

12943 12908 12843 12727 12699 12155 5944 3429 2837 2156 MS (ESI) mz 390 ([M+Na]+)

58






29




30 respectively


3276 1684 1631 1599 1518 1432 1348 1162 1089




(2H m) 205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20885 16645 14728 14557 14346

13728 13533 12935 12922 12736 12703 12552 12378 5275 3364 2545 2144 MS (FAB) mz

435 ([M+Na]+) 413 ([M+H]


+

4350991 found 4350991


3276 2928 1683 1631 1584 1511 1432 1335 1307 1249 1165 1092



59


(1H m) 13

C NMR (100 MHz CDCl3) 20919 16528 15904 14286 13759 13653 13058 12975

12912 12769 12714 12422 11392 5523 5299 3372 2519 2141 MS (FAB) mz 420 ([M+Na]+)



3269 2922 1684 1630 1583 1491 1426 1338 1162 1091 1H NMR





16579 14313 13747 13695 13600 13362 12952 12922 12872 12785 12709 12477 5285

3370 2529 2144 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3272 2921 1684 1630 1428 1338 1162 1092 1H NMR (400 MHz




(1H m) 13

C NMR (100 MHz CDCl3) 20913 16534 14287 13759 13747 13651 13548 12978

12926 12912 12714 12633 12421 5321 3370 2520 2142 2098 MS (ESI) mz 404 ([M+Na]+



3273 2922 1685 1630 1585 1488 1426 1338 1071 1011 1H NMR



60


m) 13

C NMR (100 MHz CDCl3) 20906 16581 14315 13748 13745 13593 13166 12951

12923 12818 12708 12481 12176 5292 3370 2529 2145 MS (FAB) mz 470 ([M+2+Na]+ base


[M+Na]+ 4680245 found 4682045


3271 2923 1687 1630 1585 1425 1328 1163 1121 1068 1018 1H




205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20904 16607 14322 14234 13740 13574

12986 (q J=324 Hz) 12939 12924 12703 12683 12552 (q J=27 Hz) 12506 12385 (q J=2708

Hz) 5310 3368 2535 2137 MS (FAB) mz 458 ([M+Na]+) 436 ([M+H]




3267 1685 1631 1594 1434 1339 1162 1092 1H NMR (400 MHz




C NMR (100 MHz CDCl3) 20900 16598

14315 14039 13741 13579 13450 12985 12948 12923 12788 12705 12660 12489 12462

5290 3368 2532 2143 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3261 1692 1630 1581 1491 1427 1342 1321 1162

61




m) 13

C NMR (100 MHz CDCl3) 20965 16573 14293 13732 13644 13635 13629 13093

13990 12901 12811 12740 12734 12617 12420 5106 3372 2528 2144 1981 MS (FAB) mz

404 ([M+Na]+) 382 ([M+H]


+)

4041296 found 4041296


3265 2925 1698 1677 1575 1522 1442 1346



m) 244 (3H s) 241ndash237 (2H m) 13

C NMR (100 MHz CDCl3) 20879 16906 14755 14539

14435 14204 13663 12977 12970 12805 12716 12403 12280 5878 3433 2834 2156 MS


+ 4350985

found 4350980


3263 2925 1702 1676 1611 1574 1512 1442 1329 1253 1159 1088




C NMR (100 MHz CDCl3) 20939 17019

15960 14381 14266 13687 13026 12972 12942 12828 12731 12116 11446 5895 5527


[M+Na]+ 4201240 found 4201233

62


3262 2923 1677 1575 1491 1441 1333 1160

1090 cm-1





20924 16980 14391 14234 13684 13672 13423 12966 12951 12910 12845 12716 12285

5874 3429 2835 2155 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3265 2924 1698 1677 1574 1442 1332 1188 1160 1089 1043 1H





17021 14375 14261 13839 13688 13528 12976 12966 12940 12729 12689 12128 5922




3262 3022 2871 1698 1677 1575 1488 1441 1404 1333 1160




C NMR (100 MHz CDCl3) 20914 16969

14398 14229 13723 13680 13211 12970 12955 12875 12719 12244 12187 5884 3429




63


3261 2927 1698 1677 1620 1575 1442 1327 1161





20907 16952 14403 14224 14204 13675 13041 (q J=324 Hz) 12965 12753 12715 12586




3259 2927 1700 1677 1574 1439 1334 1160

1089 cm-1





20924 16969 14406 14214 14018 13673 13486 13029 12973 12954 12852 12719 12515

12210 5887 3431 2835 2157 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]

+ base peak) HRMS



3235 2921 1690 1627 1571 1443 1320 1157 1092




C NMR (100 MHz CDCl3) 20943 17053

14368 14268 13730 13602 13575 13119 12955 12893 12835 12708 12642 12166 5563

3440 2841 2151 1875 MS (FAB) mz 404 ([M+Na]+) 382 ([M+H]


64

















65









oC
















66






6








) and α-d-27 (0169 h-1

) were

obtained











) were obtained

67

68

引用文献


2 For reviews see










136 15775ndash15780








13294ndash13297






1996 227ndash228





41 1737ndash1740




Chem 2007 72 5399ndash5402


69




1733ndash1736





Lett 2007 9 101ndash104








2000 2 3883ndash3885





Chem Soc 1984 106 3880ndash3882





2007 72 3326ndash3331




483ndash493








70


Chem 2015 13 8465ndash8469





3666ndash3667







2013 135 8063ndash8070




3576ndash3579















5206ndash5215



ndash5154



71






7187ndash7188



72

73

謝辞





































2


謝辞 73

3

理論の部

4

5

第一章緒言





















斉合成



6













た (eq 2)













7




























8




















9














10

























11












12












た









13









となった














14














15

16

















17












18

















19









20



















21







22

23























24


























25










26









27














28












29





成に優先した





30



















31









はσC-N+











32


33

第五章結論







合成























34

















35

実験の部

36

37
















38


21 Chapter 2

Synthesis of 4














yellow oil




099H) 146 (s 801H) 123 (t 73 Hz 267H) 116 (t 73 Hz 033H) 13


16847 16833 16697 16579 16451 15895 15860 13758 13719 13415 13398 13273 13256

12927 12903 12847 12820 (2 peaks) 12802 12765 12751 12744 12737 11388 11343 8136

7304 6827 6689 6168 6116 6021 5918 5510 5156 2780 1395 1376 MS (FAB) mz 498

(M+H)+ 520 (M+Na)


+ found

4982491


39










136ndash131 (6H m)










colorless oil []D18




Hz 1H) 216 (s 1H) 125 (t 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17308 15864 13786 13173

12947 12827 12756 12750 11368 7310 7106 6080 6031 5518 5133 1422 IR (neat) cmndash1

2934 2906 2864 1736 1611 1513 1458 1368 1300 1248 1185 1102 1034 MS (FAB) mz 344

(M+H) +

366 (M+Na) +


3441862 found

3441860

40




Hz 3H) 102 (s 9H) 13

C-NMR (100 MHz CDCl3) 17339 15859 13555 13552 13308 13189

12998 12933 12764 11368 6517 6193 6071 5520 5115 2666 1919 1425 IR (neat) cmndash1

MS

(FAB) mz 492 (M+H) +


4922570 found

4922570


= -52 (c 1087 CHCl3) 1H-NMR (400 MHz






Hz 51100 H) 13

C-NMR (100 MHz CDCl3) 1684 1649 1644 1628 1591 1377 1358 1334 1292

1285 1284 1283 1282 1278 1276 1275 1140 1135 732 685 621 618 613 586 552 519 140


2983 2937 1741 1655 1514 1449 1370 1251 1207 1069 1029 MS (FAB) mz

542 (M+H) +

564 (M+Na) +


5422390 found

5422394


= -40 (c 0750 CHCl3) 1H-NMR (400



(9H m) 13

C-NMR (100 MHzCDCl3) 16830 16486 16440 16275 15921 13586 13336 12934

12846 12805 11404 11357 9957 6602 6214 6186 6140 5843 5551 5533 5527 5184 1400


2983 2938 2841 1742 1655 1514 1463 1372 1253 1211 1113 1068

1039 IR (neat) cm-1

2983 2938 1742 1655 1514 1463 1372 1253 1211 1113 1068 1039 MS (FAB)

mz 496 (M+H) +


+ 4962183

found 4962182

41


= -47 (c 0597 CHCl3) 1H-NMR (400




(t J = 75 Hz 06H) 13

C-NMR (100 MHz CDCl3) 16849 16478 16449 16280 15911 13590

13559 13550 13296 13271 13264 12984 12979 12921 12831 12773 12770 11409 11385

11356 6255 6211 6176 6128 6007 5526 5159 2676 1907 1394 1388 IR (neat) cmndash1

2958

2933 2857 1739 1656 1514 1466 1426 1370 1252 1205 1178 1111 1069 1030 MS (FAB) mz 690

(M+H)+712 (M+Na)


+ 6903098 found

6903095
















64 Hz 1H) 284 (m 2H) 131ndash128 (m 12H) 13

C-NMR (100 MHz CDCl3) 17365 15879 13165

42

12958 11381 6101 6037 5531 5135 4233 3158 3094 1442 IR (neat) cmndash1

2962 2902 2836

1734 1612 1513 1462 1367 1300 1247 1178 1034 MS (FAB) mz 326 (M+H) +

348 (M+Na)+ 121 (base


3261790 found 3261786















20100 H) 136ndash108 (m 18 H) 13

C-NMR (100 MHz CDCl3) 16896 16881 16567 16548 16430 16426

16277 15941 15888 13613 13568 13426 13367 12964 12925 12879 12717 11399 11359 6215

6195 6186 6148 5987 5527 5266 4299 4285 3076 3065 2798 2764 1399 1391 1380 IR (neat)

cmndash1

2966 2904 2839 1734 1653 1514 1462 1369 1303 1253 1212 1069 1031 MS (FAB) mz 524

(M+H) +

546 (M+Na) +


5242318 found

5242313









λ = 254 nm t=169 min t=232 min []D18


43




C-NMR

(100 MHz CDCl3) 16952 16947 16715 15882 13745 12993 12881 12829 12764 12741

11359 8131 7316 710 6719 6169 5522 5165 4505 3129 2793 1412 IR (neat) cmndash1

2979

2932 2867 1764 1735 1612 1514 1455 1392 1368 1247 1154 1032 MS (FAB) mz 498 (M+H) +

520

(M+Na) +


4982492 found 4982491


t=165 min t=191 min []D18




1H) 271 (d J 78 Hz 2H) 139 (s 3H) 119 (t J 74 Hz 3H) 13


16988 16774 15891 13718 13003 12837 12824 12778 12760 11363 8129 7337 6797 6447

6162 5523 5354 4480 3090 2788 1298 IR (neat) cmndash1

2979 2931 2869 1765 1732 1612 1514

1456 1391 1367 1248 1154 1097 1063 1031 MS (FAB) mz 498 (M+H) +

520 (M+Na) +

121 (base


4982492 found 4982491







2983 2913 2845 1767 1735 1611 1588 1514 1453 1388 1247 1177 1105

1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +


(M+H) +

4362335 found 4362335





2H) 143 (s 9H) 120 (t J 73 Hz 3H) 110 (t J 69 Hz 3H) 13


17003 16786 15895 13006 12829 11360 8126 6803 6678 6443 6156 5528 5350 4478

3092 2795 1489 1400 IR (neat) cmndash1

2976 2931 2873 1762 1734 1613 1514 1461 1390 1369

1292 1244 1152 1113 1064 1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +



4362335 found 4362335

44















086 (t J = 69 Hz 3H) 081 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1696 1672 1668

1649 1594 1381 1303 1294 1285 1283 1278 1277 1139 733 711 667 623 619 616 548

547 501 453 1394 138 2 1382 IR (neat) cmndash1

2983 2935 2869 1766 1739 1612 1514 1456

1392 1369 1301 1249 1176 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +



5422390 found 5422400






J = 73 Hz 3H) 078 (t J = 73 Hz 3H) 070 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1699 1677

1671 1657 1595 1376 1305 1286 1286 1283 12804 12800 1140 7344 6705 6415 6214 6178

6152 5673 5471 4943 4461 1397 1380 1370 IR (neat) cmndash1

2983 2935 2871 1769 1735 1612 1514

1458 1391 1369 1301 1249 1178 1098 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +

121 (base peak)


5422390 found 5422393

45



= -16 (c 0719 CHCl3 96 ee) 1H-NMR (400 MHz




C-NMR (100

MHz CDCl3) 1692 1667 1666 1656 1589 1358 1357 1324 1300 1299 1278 1277 1137

668 633 621 620 617 552 529 492 449 268 192 1394 1380 137 IR (neat) cmndash1

2961

2934 2859 2369 2315 1769 1736 1650 1613 1514 1468 1428 1390 1370 1301 1251 1177 1108

1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


C38H48NO9Si (M+H) +

6903098 found 6903098







(s 9H) 099 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1695 1676 1670 1660 1589 1362

1357 1323 1318 1303 1300 1280 1278 1267 1136 639 6206 6202 614 597 552 483

441 269 190 1396 1392 136 IR (neat) cmndash1

2961 2934 2859 2369 2315 1769 1736 1650 1613

1514 1468 1428 1390 1370 1301 1251 1177 1108 1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


6903098 found 6903098


46












124 (t J = 68 Hz 3H) 114 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1697 1671 1666

1591 1304 1274 1137 655 622 6203 6196 555 553 493 453 427 320 307 139 138 IR

(neat) cmndash1

2966 2937 2868 1770 1734 1613 1514 1464 1389 1368 1301 1248 1178 1095 1033

MS (FAB) mz 524 (M+H) +

546 (M+Na) +


(M+H) +

5242318 found 5242318



= 24 (c 0551 CHCl3 91 ee) 1H-NMR (400 MHz




C-NMR (100 MHz

CDCl3) 1699 1672 1666 1654 1591 1303 1276 1137 643 6219 6219 6212 6198 560

553 485 453 428 303 291 140 138 IR (neat) cmndash1

2969 1769 1738 1613 1514 1464 1389

1369 1301 1248 1178 1034 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


mz 524 (M+H) +

546 (M+Na) +


5242318 found 5242313












47




















13659 13031 12849 12833 12805 12760 12157 12144 11379 8783 8749 7347 6855 6695 5522










b = 120516(8) Aring = 90deg

c = 271658(19) Aring = 90deg


48

Z 4



F(000) 1608















49

22 Chepter 3














122 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17340 15856 13834 13206 12945 12821

12758 12747 11357 7557 7075 6468 6064 5518 5170 1635 1421 IR (neat) cmndash1

2979 2932

2838 1734 1612 1512 1459 1373 1299 1247 1184 1159 1094 1032 MS (FAB) mz 358 (M+H) +

380 (M+Na) +


3582018 found

3582010














(m 356H) 133ndash118 (m 1115H) 111 (t J = 76 Hz 084 H) 13


50

16816 16636 16551 16455 16405 16302 16273 15888 15856 13824 13766 13612 13528

13398 13306 13096 12955 12945 12878 12832 12827 12809 12767 12757 12751 12726

12660 11377 11329 7416 7161 7135 7080 6563 6221 6195 6167 6118 5517 7167 1732

1663 1393 1385 1370 IR (neat) cmndash1

2981 2936 2905 1738 1652 1513 1457 1372 1250 1205

1177 1096 1067 1030 MS (FAB) mz 556 (M+H)+ 578 (M+Na)



5562547 found 5562547























51







13C-NMR (100 MHz CDCl3) 17382 15864 13832 13180 12947 12821 12747 11365 7634

7091 6465 6065 5522 5147 1657 1431 IR (neat) cmndash1

2979 2933 2837 1730 1611 1513 1460

1372 1302 1247 1185 1108 1033 MS (FAB) mz 358 (M+H) +

380 (M+Na) +



3582018 found 3582023









a colorless oil



oC) 737ndash720 (m


131ndash115 (m 12H) 13

C-NMR (100 MHz CDCl3) 16879 16872 16586 16491 16444 16396

16272 15920 15885 13827 13754 13584 13551 13513 13355 12972 12894 12852 12837

12824 12798 12787 12778 12749 11403 11355 7490 7341 7219 7117 6505 6219 6214

6185 6151 6112 5525 5520 5151 1641 1619 1397 1386 IR (neat) cmndash1

2982 2937 2905

1739 1656 1613 1513 1450 1373 1252 1203 1095 1070 1030 MS (FAB) mz 556 (M+H) +

578


+ found 5562549





52








094 (t J = 74 Hz 3H) 085 (t J = 74 Hz 3H) 13

C-NMR (100 MHz C6D6) 1702 1677 1673 1663

1598 1395 1308 1303 1290 1289 1281 1279 1145 784 716 713 628 625 621 5529

5526 513 465 161 1454 1450 1445 IR (neat) cmndash1

2981 2925 1766 1739 1648 1612 1514

1461 1390 1371 1301 1249 1178 1096 1031 MS (FAB) mz 556 (M+H) +



5562547 found 5562545







C-NMR (100

MHz C6D6) 1707 1671 1667 1651 1593 1387 1312 1300 1285 1283 1277 1276 1138 766

719 716 624 619 616 546 542 505 466 140 139 124 IR (neat) cmndash1

2983 2938 1766 1739

1613 1514 1459 1373 1248 1177 1148 1097 1032 MS (FAB) mz 556 (M+H) +

121 (base peak)


5562547 found 5562549




C-NMR (100

MHz CDCl3) 17035 16717 16663 16632 15871 13750 12961 12854 12832 12772 12766

11357 7216 7007 6893 6202 6187 5606 5520 4872 4588 1547 1403 1399 1396 IR (neat)

cmndash1

2983 2914 2845 1767 1735 1611 1588 1514 1453 1388 1248 1177 1105 1032 MS (FAB)

mz 556 (M+H) +


5562547 found

5562546



53





















54











3033 2359 2306

1737 1677 1610 1585 1537 1516 1486 1394 1322 1248 1179 1117 1061 1033 1006 MS (FAB) mz

1095 (M+Na) +


10949589 found

10949577







Space group C2221


b = 30665(2) Aring = 90deg

c = 134874(12) Aring = 90deg


Z 8



F(000) 4544











55











Space group C2(5)


b = 75202(3) Aring = 1025865(14)deg

c = 236650(9) Aring = 90deg


Z 8



F(000) 2368















56

23 Chapter 4















3560 3092 3010 2924 1706 1673 1627 1573 1440 1410 1346 1290












57






1H




3298 3058 2958 1678 1629 1581 1448 1419 1358




194ndash187 (1H m) 13

C NMR (100 MHz CDCl3) 20910 16553 14294 13841 13754 13634

12973 12914 12858 12767 12711 12640 12437 5337 3368 2522 2142 MS (ESI) mz 390


+ 3901134 found 3901138










3265 3028 2924 1676 1573 1494 1449 1330 1190 1159 1088 1H



245ndash228 (5H m) 13

C NMR (100 MHz CDCl3) 20938 17011 14378 14253 13821 13688 12966

12943 12908 12843 12727 12699 12155 5944 3429 2837 2156 MS (ESI) mz 390 ([M+Na]+)

58






29




30 respectively


3276 1684 1631 1599 1518 1432 1348 1162 1089




(2H m) 205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20885 16645 14728 14557 14346

13728 13533 12935 12922 12736 12703 12552 12378 5275 3364 2545 2144 MS (FAB) mz

435 ([M+Na]+) 413 ([M+H]


+

4350991 found 4350991


3276 2928 1683 1631 1584 1511 1432 1335 1307 1249 1165 1092



59


(1H m) 13

C NMR (100 MHz CDCl3) 20919 16528 15904 14286 13759 13653 13058 12975

12912 12769 12714 12422 11392 5523 5299 3372 2519 2141 MS (FAB) mz 420 ([M+Na]+)



3269 2922 1684 1630 1583 1491 1426 1338 1162 1091 1H NMR





16579 14313 13747 13695 13600 13362 12952 12922 12872 12785 12709 12477 5285

3370 2529 2144 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3272 2921 1684 1630 1428 1338 1162 1092 1H NMR (400 MHz




(1H m) 13

C NMR (100 MHz CDCl3) 20913 16534 14287 13759 13747 13651 13548 12978

12926 12912 12714 12633 12421 5321 3370 2520 2142 2098 MS (ESI) mz 404 ([M+Na]+



3273 2922 1685 1630 1585 1488 1426 1338 1071 1011 1H NMR



60


m) 13

C NMR (100 MHz CDCl3) 20906 16581 14315 13748 13745 13593 13166 12951

12923 12818 12708 12481 12176 5292 3370 2529 2145 MS (FAB) mz 470 ([M+2+Na]+ base


[M+Na]+ 4680245 found 4682045


3271 2923 1687 1630 1585 1425 1328 1163 1121 1068 1018 1H




205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20904 16607 14322 14234 13740 13574

12986 (q J=324 Hz) 12939 12924 12703 12683 12552 (q J=27 Hz) 12506 12385 (q J=2708

Hz) 5310 3368 2535 2137 MS (FAB) mz 458 ([M+Na]+) 436 ([M+H]




3267 1685 1631 1594 1434 1339 1162 1092 1H NMR (400 MHz




C NMR (100 MHz CDCl3) 20900 16598

14315 14039 13741 13579 13450 12985 12948 12923 12788 12705 12660 12489 12462

5290 3368 2532 2143 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3261 1692 1630 1581 1491 1427 1342 1321 1162

61




m) 13

C NMR (100 MHz CDCl3) 20965 16573 14293 13732 13644 13635 13629 13093

13990 12901 12811 12740 12734 12617 12420 5106 3372 2528 2144 1981 MS (FAB) mz

404 ([M+Na]+) 382 ([M+H]


+)

4041296 found 4041296


3265 2925 1698 1677 1575 1522 1442 1346



m) 244 (3H s) 241ndash237 (2H m) 13

C NMR (100 MHz CDCl3) 20879 16906 14755 14539

14435 14204 13663 12977 12970 12805 12716 12403 12280 5878 3433 2834 2156 MS


+ 4350985

found 4350980


3263 2925 1702 1676 1611 1574 1512 1442 1329 1253 1159 1088




C NMR (100 MHz CDCl3) 20939 17019

15960 14381 14266 13687 13026 12972 12942 12828 12731 12116 11446 5895 5527


[M+Na]+ 4201240 found 4201233

62


3262 2923 1677 1575 1491 1441 1333 1160

1090 cm-1





20924 16980 14391 14234 13684 13672 13423 12966 12951 12910 12845 12716 12285

5874 3429 2835 2155 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3265 2924 1698 1677 1574 1442 1332 1188 1160 1089 1043 1H





17021 14375 14261 13839 13688 13528 12976 12966 12940 12729 12689 12128 5922




3262 3022 2871 1698 1677 1575 1488 1441 1404 1333 1160




C NMR (100 MHz CDCl3) 20914 16969

14398 14229 13723 13680 13211 12970 12955 12875 12719 12244 12187 5884 3429




63


3261 2927 1698 1677 1620 1575 1442 1327 1161





20907 16952 14403 14224 14204 13675 13041 (q J=324 Hz) 12965 12753 12715 12586




3259 2927 1700 1677 1574 1439 1334 1160

1089 cm-1





20924 16969 14406 14214 14018 13673 13486 13029 12973 12954 12852 12719 12515

12210 5887 3431 2835 2157 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]

+ base peak) HRMS



3235 2921 1690 1627 1571 1443 1320 1157 1092




C NMR (100 MHz CDCl3) 20943 17053

14368 14268 13730 13602 13575 13119 12955 12893 12835 12708 12642 12166 5563

3440 2841 2151 1875 MS (FAB) mz 404 ([M+Na]+) 382 ([M+H]


64

















65









oC
















66






6








) and α-d-27 (0169 h-1

) were

obtained











) were obtained

67

68

引用文献


2 For reviews see










136 15775ndash15780








13294ndash13297






1996 227ndash228





41 1737ndash1740




Chem 2007 72 5399ndash5402


69




1733ndash1736





Lett 2007 9 101ndash104








2000 2 3883ndash3885





Chem Soc 1984 106 3880ndash3882





2007 72 3326ndash3331




483ndash493








70


Chem 2015 13 8465ndash8469





3666ndash3667







2013 135 8063ndash8070




3576ndash3579















5206ndash5215



ndash5154



71






7187ndash7188



72

73

謝辞





































3

理論の部

4

5

第一章緒言





















斉合成



6













た (eq 2)













7




























8




















9














10

























11












12












た









13









となった














14














15

16

















17












18

















19









20



















21







22

23























24


























25










26









27














28












29





成に優先した





30



















31









はσC-N+











32


33

第五章結論







合成























34

















35

実験の部

36

37
















38


21 Chapter 2

Synthesis of 4














yellow oil




099H) 146 (s 801H) 123 (t 73 Hz 267H) 116 (t 73 Hz 033H) 13


16847 16833 16697 16579 16451 15895 15860 13758 13719 13415 13398 13273 13256

12927 12903 12847 12820 (2 peaks) 12802 12765 12751 12744 12737 11388 11343 8136

7304 6827 6689 6168 6116 6021 5918 5510 5156 2780 1395 1376 MS (FAB) mz 498

(M+H)+ 520 (M+Na)


+ found

4982491


39










136ndash131 (6H m)










colorless oil []D18




Hz 1H) 216 (s 1H) 125 (t 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17308 15864 13786 13173

12947 12827 12756 12750 11368 7310 7106 6080 6031 5518 5133 1422 IR (neat) cmndash1

2934 2906 2864 1736 1611 1513 1458 1368 1300 1248 1185 1102 1034 MS (FAB) mz 344

(M+H) +

366 (M+Na) +


3441862 found

3441860

40




Hz 3H) 102 (s 9H) 13

C-NMR (100 MHz CDCl3) 17339 15859 13555 13552 13308 13189

12998 12933 12764 11368 6517 6193 6071 5520 5115 2666 1919 1425 IR (neat) cmndash1

MS

(FAB) mz 492 (M+H) +


4922570 found

4922570


= -52 (c 1087 CHCl3) 1H-NMR (400 MHz






Hz 51100 H) 13

C-NMR (100 MHz CDCl3) 1684 1649 1644 1628 1591 1377 1358 1334 1292

1285 1284 1283 1282 1278 1276 1275 1140 1135 732 685 621 618 613 586 552 519 140


2983 2937 1741 1655 1514 1449 1370 1251 1207 1069 1029 MS (FAB) mz

542 (M+H) +

564 (M+Na) +


5422390 found

5422394


= -40 (c 0750 CHCl3) 1H-NMR (400



(9H m) 13

C-NMR (100 MHzCDCl3) 16830 16486 16440 16275 15921 13586 13336 12934

12846 12805 11404 11357 9957 6602 6214 6186 6140 5843 5551 5533 5527 5184 1400


2983 2938 2841 1742 1655 1514 1463 1372 1253 1211 1113 1068

1039 IR (neat) cm-1

2983 2938 1742 1655 1514 1463 1372 1253 1211 1113 1068 1039 MS (FAB)

mz 496 (M+H) +


+ 4962183

found 4962182

41


= -47 (c 0597 CHCl3) 1H-NMR (400




(t J = 75 Hz 06H) 13

C-NMR (100 MHz CDCl3) 16849 16478 16449 16280 15911 13590

13559 13550 13296 13271 13264 12984 12979 12921 12831 12773 12770 11409 11385

11356 6255 6211 6176 6128 6007 5526 5159 2676 1907 1394 1388 IR (neat) cmndash1

2958

2933 2857 1739 1656 1514 1466 1426 1370 1252 1205 1178 1111 1069 1030 MS (FAB) mz 690

(M+H)+712 (M+Na)


+ 6903098 found

6903095
















64 Hz 1H) 284 (m 2H) 131ndash128 (m 12H) 13

C-NMR (100 MHz CDCl3) 17365 15879 13165

42

12958 11381 6101 6037 5531 5135 4233 3158 3094 1442 IR (neat) cmndash1

2962 2902 2836

1734 1612 1513 1462 1367 1300 1247 1178 1034 MS (FAB) mz 326 (M+H) +

348 (M+Na)+ 121 (base


3261790 found 3261786















20100 H) 136ndash108 (m 18 H) 13

C-NMR (100 MHz CDCl3) 16896 16881 16567 16548 16430 16426

16277 15941 15888 13613 13568 13426 13367 12964 12925 12879 12717 11399 11359 6215

6195 6186 6148 5987 5527 5266 4299 4285 3076 3065 2798 2764 1399 1391 1380 IR (neat)

cmndash1

2966 2904 2839 1734 1653 1514 1462 1369 1303 1253 1212 1069 1031 MS (FAB) mz 524

(M+H) +

546 (M+Na) +


5242318 found

5242313









λ = 254 nm t=169 min t=232 min []D18


43




C-NMR

(100 MHz CDCl3) 16952 16947 16715 15882 13745 12993 12881 12829 12764 12741

11359 8131 7316 710 6719 6169 5522 5165 4505 3129 2793 1412 IR (neat) cmndash1

2979

2932 2867 1764 1735 1612 1514 1455 1392 1368 1247 1154 1032 MS (FAB) mz 498 (M+H) +

520

(M+Na) +


4982492 found 4982491


t=165 min t=191 min []D18




1H) 271 (d J 78 Hz 2H) 139 (s 3H) 119 (t J 74 Hz 3H) 13


16988 16774 15891 13718 13003 12837 12824 12778 12760 11363 8129 7337 6797 6447

6162 5523 5354 4480 3090 2788 1298 IR (neat) cmndash1

2979 2931 2869 1765 1732 1612 1514

1456 1391 1367 1248 1154 1097 1063 1031 MS (FAB) mz 498 (M+H) +

520 (M+Na) +

121 (base


4982492 found 4982491







2983 2913 2845 1767 1735 1611 1588 1514 1453 1388 1247 1177 1105

1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +


(M+H) +

4362335 found 4362335





2H) 143 (s 9H) 120 (t J 73 Hz 3H) 110 (t J 69 Hz 3H) 13


17003 16786 15895 13006 12829 11360 8126 6803 6678 6443 6156 5528 5350 4478

3092 2795 1489 1400 IR (neat) cmndash1

2976 2931 2873 1762 1734 1613 1514 1461 1390 1369

1292 1244 1152 1113 1064 1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +



4362335 found 4362335

44















086 (t J = 69 Hz 3H) 081 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1696 1672 1668

1649 1594 1381 1303 1294 1285 1283 1278 1277 1139 733 711 667 623 619 616 548

547 501 453 1394 138 2 1382 IR (neat) cmndash1

2983 2935 2869 1766 1739 1612 1514 1456

1392 1369 1301 1249 1176 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +



5422390 found 5422400






J = 73 Hz 3H) 078 (t J = 73 Hz 3H) 070 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1699 1677

1671 1657 1595 1376 1305 1286 1286 1283 12804 12800 1140 7344 6705 6415 6214 6178

6152 5673 5471 4943 4461 1397 1380 1370 IR (neat) cmndash1

2983 2935 2871 1769 1735 1612 1514

1458 1391 1369 1301 1249 1178 1098 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +

121 (base peak)


5422390 found 5422393

45



= -16 (c 0719 CHCl3 96 ee) 1H-NMR (400 MHz




C-NMR (100

MHz CDCl3) 1692 1667 1666 1656 1589 1358 1357 1324 1300 1299 1278 1277 1137

668 633 621 620 617 552 529 492 449 268 192 1394 1380 137 IR (neat) cmndash1

2961

2934 2859 2369 2315 1769 1736 1650 1613 1514 1468 1428 1390 1370 1301 1251 1177 1108

1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


C38H48NO9Si (M+H) +

6903098 found 6903098







(s 9H) 099 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1695 1676 1670 1660 1589 1362

1357 1323 1318 1303 1300 1280 1278 1267 1136 639 6206 6202 614 597 552 483

441 269 190 1396 1392 136 IR (neat) cmndash1

2961 2934 2859 2369 2315 1769 1736 1650 1613

1514 1468 1428 1390 1370 1301 1251 1177 1108 1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


6903098 found 6903098


46












124 (t J = 68 Hz 3H) 114 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1697 1671 1666

1591 1304 1274 1137 655 622 6203 6196 555 553 493 453 427 320 307 139 138 IR

(neat) cmndash1

2966 2937 2868 1770 1734 1613 1514 1464 1389 1368 1301 1248 1178 1095 1033

MS (FAB) mz 524 (M+H) +

546 (M+Na) +


(M+H) +

5242318 found 5242318



= 24 (c 0551 CHCl3 91 ee) 1H-NMR (400 MHz




C-NMR (100 MHz

CDCl3) 1699 1672 1666 1654 1591 1303 1276 1137 643 6219 6219 6212 6198 560

553 485 453 428 303 291 140 138 IR (neat) cmndash1

2969 1769 1738 1613 1514 1464 1389

1369 1301 1248 1178 1034 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


mz 524 (M+H) +

546 (M+Na) +


5242318 found 5242313












47




















13659 13031 12849 12833 12805 12760 12157 12144 11379 8783 8749 7347 6855 6695 5522










b = 120516(8) Aring = 90deg

c = 271658(19) Aring = 90deg


48

Z 4



F(000) 1608















49

22 Chepter 3














122 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17340 15856 13834 13206 12945 12821

12758 12747 11357 7557 7075 6468 6064 5518 5170 1635 1421 IR (neat) cmndash1

2979 2932

2838 1734 1612 1512 1459 1373 1299 1247 1184 1159 1094 1032 MS (FAB) mz 358 (M+H) +

380 (M+Na) +


3582018 found

3582010














(m 356H) 133ndash118 (m 1115H) 111 (t J = 76 Hz 084 H) 13


50

16816 16636 16551 16455 16405 16302 16273 15888 15856 13824 13766 13612 13528

13398 13306 13096 12955 12945 12878 12832 12827 12809 12767 12757 12751 12726

12660 11377 11329 7416 7161 7135 7080 6563 6221 6195 6167 6118 5517 7167 1732

1663 1393 1385 1370 IR (neat) cmndash1

2981 2936 2905 1738 1652 1513 1457 1372 1250 1205

1177 1096 1067 1030 MS (FAB) mz 556 (M+H)+ 578 (M+Na)



5562547 found 5562547























51







13C-NMR (100 MHz CDCl3) 17382 15864 13832 13180 12947 12821 12747 11365 7634

7091 6465 6065 5522 5147 1657 1431 IR (neat) cmndash1

2979 2933 2837 1730 1611 1513 1460

1372 1302 1247 1185 1108 1033 MS (FAB) mz 358 (M+H) +

380 (M+Na) +



3582018 found 3582023









a colorless oil



oC) 737ndash720 (m


131ndash115 (m 12H) 13

C-NMR (100 MHz CDCl3) 16879 16872 16586 16491 16444 16396

16272 15920 15885 13827 13754 13584 13551 13513 13355 12972 12894 12852 12837

12824 12798 12787 12778 12749 11403 11355 7490 7341 7219 7117 6505 6219 6214

6185 6151 6112 5525 5520 5151 1641 1619 1397 1386 IR (neat) cmndash1

2982 2937 2905

1739 1656 1613 1513 1450 1373 1252 1203 1095 1070 1030 MS (FAB) mz 556 (M+H) +

578


+ found 5562549





52








094 (t J = 74 Hz 3H) 085 (t J = 74 Hz 3H) 13

C-NMR (100 MHz C6D6) 1702 1677 1673 1663

1598 1395 1308 1303 1290 1289 1281 1279 1145 784 716 713 628 625 621 5529

5526 513 465 161 1454 1450 1445 IR (neat) cmndash1

2981 2925 1766 1739 1648 1612 1514

1461 1390 1371 1301 1249 1178 1096 1031 MS (FAB) mz 556 (M+H) +



5562547 found 5562545







C-NMR (100

MHz C6D6) 1707 1671 1667 1651 1593 1387 1312 1300 1285 1283 1277 1276 1138 766

719 716 624 619 616 546 542 505 466 140 139 124 IR (neat) cmndash1

2983 2938 1766 1739

1613 1514 1459 1373 1248 1177 1148 1097 1032 MS (FAB) mz 556 (M+H) +

121 (base peak)


5562547 found 5562549




C-NMR (100

MHz CDCl3) 17035 16717 16663 16632 15871 13750 12961 12854 12832 12772 12766

11357 7216 7007 6893 6202 6187 5606 5520 4872 4588 1547 1403 1399 1396 IR (neat)

cmndash1

2983 2914 2845 1767 1735 1611 1588 1514 1453 1388 1248 1177 1105 1032 MS (FAB)

mz 556 (M+H) +


5562547 found

5562546



53





















54











3033 2359 2306

1737 1677 1610 1585 1537 1516 1486 1394 1322 1248 1179 1117 1061 1033 1006 MS (FAB) mz

1095 (M+Na) +


10949589 found

10949577







Space group C2221


b = 30665(2) Aring = 90deg

c = 134874(12) Aring = 90deg


Z 8



F(000) 4544











55











Space group C2(5)


b = 75202(3) Aring = 1025865(14)deg

c = 236650(9) Aring = 90deg


Z 8



F(000) 2368















56

23 Chapter 4















3560 3092 3010 2924 1706 1673 1627 1573 1440 1410 1346 1290












57






1H




3298 3058 2958 1678 1629 1581 1448 1419 1358




194ndash187 (1H m) 13

C NMR (100 MHz CDCl3) 20910 16553 14294 13841 13754 13634

12973 12914 12858 12767 12711 12640 12437 5337 3368 2522 2142 MS (ESI) mz 390


+ 3901134 found 3901138










3265 3028 2924 1676 1573 1494 1449 1330 1190 1159 1088 1H



245ndash228 (5H m) 13

C NMR (100 MHz CDCl3) 20938 17011 14378 14253 13821 13688 12966

12943 12908 12843 12727 12699 12155 5944 3429 2837 2156 MS (ESI) mz 390 ([M+Na]+)

58






29




30 respectively


3276 1684 1631 1599 1518 1432 1348 1162 1089




(2H m) 205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20885 16645 14728 14557 14346

13728 13533 12935 12922 12736 12703 12552 12378 5275 3364 2545 2144 MS (FAB) mz

435 ([M+Na]+) 413 ([M+H]


+

4350991 found 4350991


3276 2928 1683 1631 1584 1511 1432 1335 1307 1249 1165 1092



59


(1H m) 13

C NMR (100 MHz CDCl3) 20919 16528 15904 14286 13759 13653 13058 12975

12912 12769 12714 12422 11392 5523 5299 3372 2519 2141 MS (FAB) mz 420 ([M+Na]+)



3269 2922 1684 1630 1583 1491 1426 1338 1162 1091 1H NMR





16579 14313 13747 13695 13600 13362 12952 12922 12872 12785 12709 12477 5285

3370 2529 2144 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3272 2921 1684 1630 1428 1338 1162 1092 1H NMR (400 MHz




(1H m) 13

C NMR (100 MHz CDCl3) 20913 16534 14287 13759 13747 13651 13548 12978

12926 12912 12714 12633 12421 5321 3370 2520 2142 2098 MS (ESI) mz 404 ([M+Na]+



3273 2922 1685 1630 1585 1488 1426 1338 1071 1011 1H NMR



60


m) 13

C NMR (100 MHz CDCl3) 20906 16581 14315 13748 13745 13593 13166 12951

12923 12818 12708 12481 12176 5292 3370 2529 2145 MS (FAB) mz 470 ([M+2+Na]+ base


[M+Na]+ 4680245 found 4682045


3271 2923 1687 1630 1585 1425 1328 1163 1121 1068 1018 1H




205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20904 16607 14322 14234 13740 13574

12986 (q J=324 Hz) 12939 12924 12703 12683 12552 (q J=27 Hz) 12506 12385 (q J=2708

Hz) 5310 3368 2535 2137 MS (FAB) mz 458 ([M+Na]+) 436 ([M+H]




3267 1685 1631 1594 1434 1339 1162 1092 1H NMR (400 MHz




C NMR (100 MHz CDCl3) 20900 16598

14315 14039 13741 13579 13450 12985 12948 12923 12788 12705 12660 12489 12462

5290 3368 2532 2143 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3261 1692 1630 1581 1491 1427 1342 1321 1162

61




m) 13

C NMR (100 MHz CDCl3) 20965 16573 14293 13732 13644 13635 13629 13093

13990 12901 12811 12740 12734 12617 12420 5106 3372 2528 2144 1981 MS (FAB) mz

404 ([M+Na]+) 382 ([M+H]


+)

4041296 found 4041296


3265 2925 1698 1677 1575 1522 1442 1346



m) 244 (3H s) 241ndash237 (2H m) 13

C NMR (100 MHz CDCl3) 20879 16906 14755 14539

14435 14204 13663 12977 12970 12805 12716 12403 12280 5878 3433 2834 2156 MS


+ 4350985

found 4350980


3263 2925 1702 1676 1611 1574 1512 1442 1329 1253 1159 1088




C NMR (100 MHz CDCl3) 20939 17019

15960 14381 14266 13687 13026 12972 12942 12828 12731 12116 11446 5895 5527


[M+Na]+ 4201240 found 4201233

62


3262 2923 1677 1575 1491 1441 1333 1160

1090 cm-1





20924 16980 14391 14234 13684 13672 13423 12966 12951 12910 12845 12716 12285

5874 3429 2835 2155 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3265 2924 1698 1677 1574 1442 1332 1188 1160 1089 1043 1H





17021 14375 14261 13839 13688 13528 12976 12966 12940 12729 12689 12128 5922




3262 3022 2871 1698 1677 1575 1488 1441 1404 1333 1160




C NMR (100 MHz CDCl3) 20914 16969

14398 14229 13723 13680 13211 12970 12955 12875 12719 12244 12187 5884 3429




63


3261 2927 1698 1677 1620 1575 1442 1327 1161





20907 16952 14403 14224 14204 13675 13041 (q J=324 Hz) 12965 12753 12715 12586




3259 2927 1700 1677 1574 1439 1334 1160

1089 cm-1





20924 16969 14406 14214 14018 13673 13486 13029 12973 12954 12852 12719 12515

12210 5887 3431 2835 2157 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]

+ base peak) HRMS



3235 2921 1690 1627 1571 1443 1320 1157 1092




C NMR (100 MHz CDCl3) 20943 17053

14368 14268 13730 13602 13575 13119 12955 12893 12835 12708 12642 12166 5563

3440 2841 2151 1875 MS (FAB) mz 404 ([M+Na]+) 382 ([M+H]


64

















65









oC
















66






6








) and α-d-27 (0169 h-1

) were

obtained











) were obtained

67

68

引用文献


2 For reviews see










136 15775ndash15780








13294ndash13297






1996 227ndash228





41 1737ndash1740




Chem 2007 72 5399ndash5402


69




1733ndash1736





Lett 2007 9 101ndash104








2000 2 3883ndash3885





Chem Soc 1984 106 3880ndash3882





2007 72 3326ndash3331




483ndash493








70


Chem 2015 13 8465ndash8469





3666ndash3667







2013 135 8063ndash8070




3576ndash3579















5206ndash5215



ndash5154



71






7187ndash7188



72

73

謝辞





































4

5

第一章緒言





















斉合成



6













た (eq 2)













7




























8




















9














10

























11












12












た









13









となった














14














15

16

















17












18

















19









20



















21







22

23























24


























25










26









27














28












29





成に優先した





30



















31









はσC-N+











32


33

第五章結論







合成























34

















35

実験の部

36

37
















38


21 Chapter 2

Synthesis of 4














yellow oil




099H) 146 (s 801H) 123 (t 73 Hz 267H) 116 (t 73 Hz 033H) 13


16847 16833 16697 16579 16451 15895 15860 13758 13719 13415 13398 13273 13256

12927 12903 12847 12820 (2 peaks) 12802 12765 12751 12744 12737 11388 11343 8136

7304 6827 6689 6168 6116 6021 5918 5510 5156 2780 1395 1376 MS (FAB) mz 498

(M+H)+ 520 (M+Na)


+ found

4982491


39










136ndash131 (6H m)










colorless oil []D18




Hz 1H) 216 (s 1H) 125 (t 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17308 15864 13786 13173

12947 12827 12756 12750 11368 7310 7106 6080 6031 5518 5133 1422 IR (neat) cmndash1

2934 2906 2864 1736 1611 1513 1458 1368 1300 1248 1185 1102 1034 MS (FAB) mz 344

(M+H) +

366 (M+Na) +


3441862 found

3441860

40




Hz 3H) 102 (s 9H) 13

C-NMR (100 MHz CDCl3) 17339 15859 13555 13552 13308 13189

12998 12933 12764 11368 6517 6193 6071 5520 5115 2666 1919 1425 IR (neat) cmndash1

MS

(FAB) mz 492 (M+H) +


4922570 found

4922570


= -52 (c 1087 CHCl3) 1H-NMR (400 MHz






Hz 51100 H) 13

C-NMR (100 MHz CDCl3) 1684 1649 1644 1628 1591 1377 1358 1334 1292

1285 1284 1283 1282 1278 1276 1275 1140 1135 732 685 621 618 613 586 552 519 140


2983 2937 1741 1655 1514 1449 1370 1251 1207 1069 1029 MS (FAB) mz

542 (M+H) +

564 (M+Na) +


5422390 found

5422394


= -40 (c 0750 CHCl3) 1H-NMR (400



(9H m) 13

C-NMR (100 MHzCDCl3) 16830 16486 16440 16275 15921 13586 13336 12934

12846 12805 11404 11357 9957 6602 6214 6186 6140 5843 5551 5533 5527 5184 1400


2983 2938 2841 1742 1655 1514 1463 1372 1253 1211 1113 1068

1039 IR (neat) cm-1

2983 2938 1742 1655 1514 1463 1372 1253 1211 1113 1068 1039 MS (FAB)

mz 496 (M+H) +


+ 4962183

found 4962182

41


= -47 (c 0597 CHCl3) 1H-NMR (400




(t J = 75 Hz 06H) 13

C-NMR (100 MHz CDCl3) 16849 16478 16449 16280 15911 13590

13559 13550 13296 13271 13264 12984 12979 12921 12831 12773 12770 11409 11385

11356 6255 6211 6176 6128 6007 5526 5159 2676 1907 1394 1388 IR (neat) cmndash1

2958

2933 2857 1739 1656 1514 1466 1426 1370 1252 1205 1178 1111 1069 1030 MS (FAB) mz 690

(M+H)+712 (M+Na)


+ 6903098 found

6903095
















64 Hz 1H) 284 (m 2H) 131ndash128 (m 12H) 13

C-NMR (100 MHz CDCl3) 17365 15879 13165

42

12958 11381 6101 6037 5531 5135 4233 3158 3094 1442 IR (neat) cmndash1

2962 2902 2836

1734 1612 1513 1462 1367 1300 1247 1178 1034 MS (FAB) mz 326 (M+H) +

348 (M+Na)+ 121 (base


3261790 found 3261786















20100 H) 136ndash108 (m 18 H) 13

C-NMR (100 MHz CDCl3) 16896 16881 16567 16548 16430 16426

16277 15941 15888 13613 13568 13426 13367 12964 12925 12879 12717 11399 11359 6215

6195 6186 6148 5987 5527 5266 4299 4285 3076 3065 2798 2764 1399 1391 1380 IR (neat)

cmndash1

2966 2904 2839 1734 1653 1514 1462 1369 1303 1253 1212 1069 1031 MS (FAB) mz 524

(M+H) +

546 (M+Na) +


5242318 found

5242313









λ = 254 nm t=169 min t=232 min []D18


43




C-NMR

(100 MHz CDCl3) 16952 16947 16715 15882 13745 12993 12881 12829 12764 12741

11359 8131 7316 710 6719 6169 5522 5165 4505 3129 2793 1412 IR (neat) cmndash1

2979

2932 2867 1764 1735 1612 1514 1455 1392 1368 1247 1154 1032 MS (FAB) mz 498 (M+H) +

520

(M+Na) +


4982492 found 4982491


t=165 min t=191 min []D18




1H) 271 (d J 78 Hz 2H) 139 (s 3H) 119 (t J 74 Hz 3H) 13


16988 16774 15891 13718 13003 12837 12824 12778 12760 11363 8129 7337 6797 6447

6162 5523 5354 4480 3090 2788 1298 IR (neat) cmndash1

2979 2931 2869 1765 1732 1612 1514

1456 1391 1367 1248 1154 1097 1063 1031 MS (FAB) mz 498 (M+H) +

520 (M+Na) +

121 (base


4982492 found 4982491







2983 2913 2845 1767 1735 1611 1588 1514 1453 1388 1247 1177 1105

1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +


(M+H) +

4362335 found 4362335





2H) 143 (s 9H) 120 (t J 73 Hz 3H) 110 (t J 69 Hz 3H) 13


17003 16786 15895 13006 12829 11360 8126 6803 6678 6443 6156 5528 5350 4478

3092 2795 1489 1400 IR (neat) cmndash1

2976 2931 2873 1762 1734 1613 1514 1461 1390 1369

1292 1244 1152 1113 1064 1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +



4362335 found 4362335

44















086 (t J = 69 Hz 3H) 081 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1696 1672 1668

1649 1594 1381 1303 1294 1285 1283 1278 1277 1139 733 711 667 623 619 616 548

547 501 453 1394 138 2 1382 IR (neat) cmndash1

2983 2935 2869 1766 1739 1612 1514 1456

1392 1369 1301 1249 1176 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +



5422390 found 5422400






J = 73 Hz 3H) 078 (t J = 73 Hz 3H) 070 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1699 1677

1671 1657 1595 1376 1305 1286 1286 1283 12804 12800 1140 7344 6705 6415 6214 6178

6152 5673 5471 4943 4461 1397 1380 1370 IR (neat) cmndash1

2983 2935 2871 1769 1735 1612 1514

1458 1391 1369 1301 1249 1178 1098 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +

121 (base peak)


5422390 found 5422393

45



= -16 (c 0719 CHCl3 96 ee) 1H-NMR (400 MHz




C-NMR (100

MHz CDCl3) 1692 1667 1666 1656 1589 1358 1357 1324 1300 1299 1278 1277 1137

668 633 621 620 617 552 529 492 449 268 192 1394 1380 137 IR (neat) cmndash1

2961

2934 2859 2369 2315 1769 1736 1650 1613 1514 1468 1428 1390 1370 1301 1251 1177 1108

1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


C38H48NO9Si (M+H) +

6903098 found 6903098







(s 9H) 099 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1695 1676 1670 1660 1589 1362

1357 1323 1318 1303 1300 1280 1278 1267 1136 639 6206 6202 614 597 552 483

441 269 190 1396 1392 136 IR (neat) cmndash1

2961 2934 2859 2369 2315 1769 1736 1650 1613

1514 1468 1428 1390 1370 1301 1251 1177 1108 1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


6903098 found 6903098


46












124 (t J = 68 Hz 3H) 114 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1697 1671 1666

1591 1304 1274 1137 655 622 6203 6196 555 553 493 453 427 320 307 139 138 IR

(neat) cmndash1

2966 2937 2868 1770 1734 1613 1514 1464 1389 1368 1301 1248 1178 1095 1033

MS (FAB) mz 524 (M+H) +

546 (M+Na) +


(M+H) +

5242318 found 5242318



= 24 (c 0551 CHCl3 91 ee) 1H-NMR (400 MHz




C-NMR (100 MHz

CDCl3) 1699 1672 1666 1654 1591 1303 1276 1137 643 6219 6219 6212 6198 560

553 485 453 428 303 291 140 138 IR (neat) cmndash1

2969 1769 1738 1613 1514 1464 1389

1369 1301 1248 1178 1034 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


mz 524 (M+H) +

546 (M+Na) +


5242318 found 5242313












47




















13659 13031 12849 12833 12805 12760 12157 12144 11379 8783 8749 7347 6855 6695 5522










b = 120516(8) Aring = 90deg

c = 271658(19) Aring = 90deg


48

Z 4



F(000) 1608















49

22 Chepter 3














122 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17340 15856 13834 13206 12945 12821

12758 12747 11357 7557 7075 6468 6064 5518 5170 1635 1421 IR (neat) cmndash1

2979 2932

2838 1734 1612 1512 1459 1373 1299 1247 1184 1159 1094 1032 MS (FAB) mz 358 (M+H) +

380 (M+Na) +


3582018 found

3582010














(m 356H) 133ndash118 (m 1115H) 111 (t J = 76 Hz 084 H) 13


50

16816 16636 16551 16455 16405 16302 16273 15888 15856 13824 13766 13612 13528

13398 13306 13096 12955 12945 12878 12832 12827 12809 12767 12757 12751 12726

12660 11377 11329 7416 7161 7135 7080 6563 6221 6195 6167 6118 5517 7167 1732

1663 1393 1385 1370 IR (neat) cmndash1

2981 2936 2905 1738 1652 1513 1457 1372 1250 1205

1177 1096 1067 1030 MS (FAB) mz 556 (M+H)+ 578 (M+Na)



5562547 found 5562547























51







13C-NMR (100 MHz CDCl3) 17382 15864 13832 13180 12947 12821 12747 11365 7634

7091 6465 6065 5522 5147 1657 1431 IR (neat) cmndash1

2979 2933 2837 1730 1611 1513 1460

1372 1302 1247 1185 1108 1033 MS (FAB) mz 358 (M+H) +

380 (M+Na) +



3582018 found 3582023









a colorless oil



oC) 737ndash720 (m


131ndash115 (m 12H) 13

C-NMR (100 MHz CDCl3) 16879 16872 16586 16491 16444 16396

16272 15920 15885 13827 13754 13584 13551 13513 13355 12972 12894 12852 12837

12824 12798 12787 12778 12749 11403 11355 7490 7341 7219 7117 6505 6219 6214

6185 6151 6112 5525 5520 5151 1641 1619 1397 1386 IR (neat) cmndash1

2982 2937 2905

1739 1656 1613 1513 1450 1373 1252 1203 1095 1070 1030 MS (FAB) mz 556 (M+H) +

578


+ found 5562549





52








094 (t J = 74 Hz 3H) 085 (t J = 74 Hz 3H) 13

C-NMR (100 MHz C6D6) 1702 1677 1673 1663

1598 1395 1308 1303 1290 1289 1281 1279 1145 784 716 713 628 625 621 5529

5526 513 465 161 1454 1450 1445 IR (neat) cmndash1

2981 2925 1766 1739 1648 1612 1514

1461 1390 1371 1301 1249 1178 1096 1031 MS (FAB) mz 556 (M+H) +



5562547 found 5562545







C-NMR (100

MHz C6D6) 1707 1671 1667 1651 1593 1387 1312 1300 1285 1283 1277 1276 1138 766

719 716 624 619 616 546 542 505 466 140 139 124 IR (neat) cmndash1

2983 2938 1766 1739

1613 1514 1459 1373 1248 1177 1148 1097 1032 MS (FAB) mz 556 (M+H) +

121 (base peak)


5562547 found 5562549




C-NMR (100

MHz CDCl3) 17035 16717 16663 16632 15871 13750 12961 12854 12832 12772 12766

11357 7216 7007 6893 6202 6187 5606 5520 4872 4588 1547 1403 1399 1396 IR (neat)

cmndash1

2983 2914 2845 1767 1735 1611 1588 1514 1453 1388 1248 1177 1105 1032 MS (FAB)

mz 556 (M+H) +


5562547 found

5562546



53





















54











3033 2359 2306

1737 1677 1610 1585 1537 1516 1486 1394 1322 1248 1179 1117 1061 1033 1006 MS (FAB) mz

1095 (M+Na) +


10949589 found

10949577







Space group C2221


b = 30665(2) Aring = 90deg

c = 134874(12) Aring = 90deg


Z 8



F(000) 4544











55











Space group C2(5)


b = 75202(3) Aring = 1025865(14)deg

c = 236650(9) Aring = 90deg


Z 8



F(000) 2368















56

23 Chapter 4















3560 3092 3010 2924 1706 1673 1627 1573 1440 1410 1346 1290












57






1H




3298 3058 2958 1678 1629 1581 1448 1419 1358




194ndash187 (1H m) 13

C NMR (100 MHz CDCl3) 20910 16553 14294 13841 13754 13634

12973 12914 12858 12767 12711 12640 12437 5337 3368 2522 2142 MS (ESI) mz 390


+ 3901134 found 3901138










3265 3028 2924 1676 1573 1494 1449 1330 1190 1159 1088 1H



245ndash228 (5H m) 13

C NMR (100 MHz CDCl3) 20938 17011 14378 14253 13821 13688 12966

12943 12908 12843 12727 12699 12155 5944 3429 2837 2156 MS (ESI) mz 390 ([M+Na]+)

58






29




30 respectively


3276 1684 1631 1599 1518 1432 1348 1162 1089




(2H m) 205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20885 16645 14728 14557 14346

13728 13533 12935 12922 12736 12703 12552 12378 5275 3364 2545 2144 MS (FAB) mz

435 ([M+Na]+) 413 ([M+H]


+

4350991 found 4350991


3276 2928 1683 1631 1584 1511 1432 1335 1307 1249 1165 1092



59


(1H m) 13

C NMR (100 MHz CDCl3) 20919 16528 15904 14286 13759 13653 13058 12975

12912 12769 12714 12422 11392 5523 5299 3372 2519 2141 MS (FAB) mz 420 ([M+Na]+)



3269 2922 1684 1630 1583 1491 1426 1338 1162 1091 1H NMR





16579 14313 13747 13695 13600 13362 12952 12922 12872 12785 12709 12477 5285

3370 2529 2144 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3272 2921 1684 1630 1428 1338 1162 1092 1H NMR (400 MHz




(1H m) 13

C NMR (100 MHz CDCl3) 20913 16534 14287 13759 13747 13651 13548 12978

12926 12912 12714 12633 12421 5321 3370 2520 2142 2098 MS (ESI) mz 404 ([M+Na]+



3273 2922 1685 1630 1585 1488 1426 1338 1071 1011 1H NMR



60


m) 13

C NMR (100 MHz CDCl3) 20906 16581 14315 13748 13745 13593 13166 12951

12923 12818 12708 12481 12176 5292 3370 2529 2145 MS (FAB) mz 470 ([M+2+Na]+ base


[M+Na]+ 4680245 found 4682045


3271 2923 1687 1630 1585 1425 1328 1163 1121 1068 1018 1H




205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20904 16607 14322 14234 13740 13574

12986 (q J=324 Hz) 12939 12924 12703 12683 12552 (q J=27 Hz) 12506 12385 (q J=2708

Hz) 5310 3368 2535 2137 MS (FAB) mz 458 ([M+Na]+) 436 ([M+H]




3267 1685 1631 1594 1434 1339 1162 1092 1H NMR (400 MHz




C NMR (100 MHz CDCl3) 20900 16598

14315 14039 13741 13579 13450 12985 12948 12923 12788 12705 12660 12489 12462

5290 3368 2532 2143 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3261 1692 1630 1581 1491 1427 1342 1321 1162

61




m) 13

C NMR (100 MHz CDCl3) 20965 16573 14293 13732 13644 13635 13629 13093

13990 12901 12811 12740 12734 12617 12420 5106 3372 2528 2144 1981 MS (FAB) mz

404 ([M+Na]+) 382 ([M+H]


+)

4041296 found 4041296


3265 2925 1698 1677 1575 1522 1442 1346



m) 244 (3H s) 241ndash237 (2H m) 13

C NMR (100 MHz CDCl3) 20879 16906 14755 14539

14435 14204 13663 12977 12970 12805 12716 12403 12280 5878 3433 2834 2156 MS


+ 4350985

found 4350980


3263 2925 1702 1676 1611 1574 1512 1442 1329 1253 1159 1088




C NMR (100 MHz CDCl3) 20939 17019

15960 14381 14266 13687 13026 12972 12942 12828 12731 12116 11446 5895 5527


[M+Na]+ 4201240 found 4201233

62


3262 2923 1677 1575 1491 1441 1333 1160

1090 cm-1





20924 16980 14391 14234 13684 13672 13423 12966 12951 12910 12845 12716 12285

5874 3429 2835 2155 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3265 2924 1698 1677 1574 1442 1332 1188 1160 1089 1043 1H





17021 14375 14261 13839 13688 13528 12976 12966 12940 12729 12689 12128 5922




3262 3022 2871 1698 1677 1575 1488 1441 1404 1333 1160




C NMR (100 MHz CDCl3) 20914 16969

14398 14229 13723 13680 13211 12970 12955 12875 12719 12244 12187 5884 3429




63


3261 2927 1698 1677 1620 1575 1442 1327 1161





20907 16952 14403 14224 14204 13675 13041 (q J=324 Hz) 12965 12753 12715 12586




3259 2927 1700 1677 1574 1439 1334 1160

1089 cm-1





20924 16969 14406 14214 14018 13673 13486 13029 12973 12954 12852 12719 12515

12210 5887 3431 2835 2157 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]

+ base peak) HRMS



3235 2921 1690 1627 1571 1443 1320 1157 1092




C NMR (100 MHz CDCl3) 20943 17053

14368 14268 13730 13602 13575 13119 12955 12893 12835 12708 12642 12166 5563

3440 2841 2151 1875 MS (FAB) mz 404 ([M+Na]+) 382 ([M+H]


64

















65









oC
















66






6








) and α-d-27 (0169 h-1

) were

obtained











) were obtained

67

68

引用文献


2 For reviews see










136 15775ndash15780








13294ndash13297






1996 227ndash228





41 1737ndash1740




Chem 2007 72 5399ndash5402


69




1733ndash1736





Lett 2007 9 101ndash104








2000 2 3883ndash3885





Chem Soc 1984 106 3880ndash3882





2007 72 3326ndash3331




483ndash493








70


Chem 2015 13 8465ndash8469





3666ndash3667







2013 135 8063ndash8070




3576ndash3579















5206ndash5215



ndash5154



71






7187ndash7188



72

73

謝辞





































5

第一章緒言





















斉合成



6













た (eq 2)













7




























8




















9














10

























11












12












た









13









となった














14














15

16

















17












18

















19









20



















21







22

23























24


























25










26









27














28












29





成に優先した





30



















31









はσC-N+











32


33

第五章結論







合成























34

















35

実験の部

36

37
















38


21 Chapter 2

Synthesis of 4














yellow oil




099H) 146 (s 801H) 123 (t 73 Hz 267H) 116 (t 73 Hz 033H) 13


16847 16833 16697 16579 16451 15895 15860 13758 13719 13415 13398 13273 13256

12927 12903 12847 12820 (2 peaks) 12802 12765 12751 12744 12737 11388 11343 8136

7304 6827 6689 6168 6116 6021 5918 5510 5156 2780 1395 1376 MS (FAB) mz 498

(M+H)+ 520 (M+Na)


+ found

4982491


39










136ndash131 (6H m)










colorless oil []D18




Hz 1H) 216 (s 1H) 125 (t 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17308 15864 13786 13173

12947 12827 12756 12750 11368 7310 7106 6080 6031 5518 5133 1422 IR (neat) cmndash1

2934 2906 2864 1736 1611 1513 1458 1368 1300 1248 1185 1102 1034 MS (FAB) mz 344

(M+H) +

366 (M+Na) +


3441862 found

3441860

40




Hz 3H) 102 (s 9H) 13

C-NMR (100 MHz CDCl3) 17339 15859 13555 13552 13308 13189

12998 12933 12764 11368 6517 6193 6071 5520 5115 2666 1919 1425 IR (neat) cmndash1

MS

(FAB) mz 492 (M+H) +


4922570 found

4922570


= -52 (c 1087 CHCl3) 1H-NMR (400 MHz






Hz 51100 H) 13

C-NMR (100 MHz CDCl3) 1684 1649 1644 1628 1591 1377 1358 1334 1292

1285 1284 1283 1282 1278 1276 1275 1140 1135 732 685 621 618 613 586 552 519 140


2983 2937 1741 1655 1514 1449 1370 1251 1207 1069 1029 MS (FAB) mz

542 (M+H) +

564 (M+Na) +


5422390 found

5422394


= -40 (c 0750 CHCl3) 1H-NMR (400



(9H m) 13

C-NMR (100 MHzCDCl3) 16830 16486 16440 16275 15921 13586 13336 12934

12846 12805 11404 11357 9957 6602 6214 6186 6140 5843 5551 5533 5527 5184 1400


2983 2938 2841 1742 1655 1514 1463 1372 1253 1211 1113 1068

1039 IR (neat) cm-1

2983 2938 1742 1655 1514 1463 1372 1253 1211 1113 1068 1039 MS (FAB)

mz 496 (M+H) +


+ 4962183

found 4962182

41


= -47 (c 0597 CHCl3) 1H-NMR (400




(t J = 75 Hz 06H) 13

C-NMR (100 MHz CDCl3) 16849 16478 16449 16280 15911 13590

13559 13550 13296 13271 13264 12984 12979 12921 12831 12773 12770 11409 11385

11356 6255 6211 6176 6128 6007 5526 5159 2676 1907 1394 1388 IR (neat) cmndash1

2958

2933 2857 1739 1656 1514 1466 1426 1370 1252 1205 1178 1111 1069 1030 MS (FAB) mz 690

(M+H)+712 (M+Na)


+ 6903098 found

6903095
















64 Hz 1H) 284 (m 2H) 131ndash128 (m 12H) 13

C-NMR (100 MHz CDCl3) 17365 15879 13165

42

12958 11381 6101 6037 5531 5135 4233 3158 3094 1442 IR (neat) cmndash1

2962 2902 2836

1734 1612 1513 1462 1367 1300 1247 1178 1034 MS (FAB) mz 326 (M+H) +

348 (M+Na)+ 121 (base


3261790 found 3261786















20100 H) 136ndash108 (m 18 H) 13

C-NMR (100 MHz CDCl3) 16896 16881 16567 16548 16430 16426

16277 15941 15888 13613 13568 13426 13367 12964 12925 12879 12717 11399 11359 6215

6195 6186 6148 5987 5527 5266 4299 4285 3076 3065 2798 2764 1399 1391 1380 IR (neat)

cmndash1

2966 2904 2839 1734 1653 1514 1462 1369 1303 1253 1212 1069 1031 MS (FAB) mz 524

(M+H) +

546 (M+Na) +


5242318 found

5242313









λ = 254 nm t=169 min t=232 min []D18


43




C-NMR

(100 MHz CDCl3) 16952 16947 16715 15882 13745 12993 12881 12829 12764 12741

11359 8131 7316 710 6719 6169 5522 5165 4505 3129 2793 1412 IR (neat) cmndash1

2979

2932 2867 1764 1735 1612 1514 1455 1392 1368 1247 1154 1032 MS (FAB) mz 498 (M+H) +

520

(M+Na) +


4982492 found 4982491


t=165 min t=191 min []D18




1H) 271 (d J 78 Hz 2H) 139 (s 3H) 119 (t J 74 Hz 3H) 13


16988 16774 15891 13718 13003 12837 12824 12778 12760 11363 8129 7337 6797 6447

6162 5523 5354 4480 3090 2788 1298 IR (neat) cmndash1

2979 2931 2869 1765 1732 1612 1514

1456 1391 1367 1248 1154 1097 1063 1031 MS (FAB) mz 498 (M+H) +

520 (M+Na) +

121 (base


4982492 found 4982491







2983 2913 2845 1767 1735 1611 1588 1514 1453 1388 1247 1177 1105

1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +


(M+H) +

4362335 found 4362335





2H) 143 (s 9H) 120 (t J 73 Hz 3H) 110 (t J 69 Hz 3H) 13


17003 16786 15895 13006 12829 11360 8126 6803 6678 6443 6156 5528 5350 4478

3092 2795 1489 1400 IR (neat) cmndash1

2976 2931 2873 1762 1734 1613 1514 1461 1390 1369

1292 1244 1152 1113 1064 1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +



4362335 found 4362335

44















086 (t J = 69 Hz 3H) 081 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1696 1672 1668

1649 1594 1381 1303 1294 1285 1283 1278 1277 1139 733 711 667 623 619 616 548

547 501 453 1394 138 2 1382 IR (neat) cmndash1

2983 2935 2869 1766 1739 1612 1514 1456

1392 1369 1301 1249 1176 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +



5422390 found 5422400






J = 73 Hz 3H) 078 (t J = 73 Hz 3H) 070 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1699 1677

1671 1657 1595 1376 1305 1286 1286 1283 12804 12800 1140 7344 6705 6415 6214 6178

6152 5673 5471 4943 4461 1397 1380 1370 IR (neat) cmndash1

2983 2935 2871 1769 1735 1612 1514

1458 1391 1369 1301 1249 1178 1098 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +

121 (base peak)


5422390 found 5422393

45



= -16 (c 0719 CHCl3 96 ee) 1H-NMR (400 MHz




C-NMR (100

MHz CDCl3) 1692 1667 1666 1656 1589 1358 1357 1324 1300 1299 1278 1277 1137

668 633 621 620 617 552 529 492 449 268 192 1394 1380 137 IR (neat) cmndash1

2961

2934 2859 2369 2315 1769 1736 1650 1613 1514 1468 1428 1390 1370 1301 1251 1177 1108

1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


C38H48NO9Si (M+H) +

6903098 found 6903098







(s 9H) 099 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1695 1676 1670 1660 1589 1362

1357 1323 1318 1303 1300 1280 1278 1267 1136 639 6206 6202 614 597 552 483

441 269 190 1396 1392 136 IR (neat) cmndash1

2961 2934 2859 2369 2315 1769 1736 1650 1613

1514 1468 1428 1390 1370 1301 1251 1177 1108 1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


6903098 found 6903098


46












124 (t J = 68 Hz 3H) 114 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1697 1671 1666

1591 1304 1274 1137 655 622 6203 6196 555 553 493 453 427 320 307 139 138 IR

(neat) cmndash1

2966 2937 2868 1770 1734 1613 1514 1464 1389 1368 1301 1248 1178 1095 1033

MS (FAB) mz 524 (M+H) +

546 (M+Na) +


(M+H) +

5242318 found 5242318



= 24 (c 0551 CHCl3 91 ee) 1H-NMR (400 MHz




C-NMR (100 MHz

CDCl3) 1699 1672 1666 1654 1591 1303 1276 1137 643 6219 6219 6212 6198 560

553 485 453 428 303 291 140 138 IR (neat) cmndash1

2969 1769 1738 1613 1514 1464 1389

1369 1301 1248 1178 1034 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


mz 524 (M+H) +

546 (M+Na) +


5242318 found 5242313












47




















13659 13031 12849 12833 12805 12760 12157 12144 11379 8783 8749 7347 6855 6695 5522










b = 120516(8) Aring = 90deg

c = 271658(19) Aring = 90deg


48

Z 4



F(000) 1608















49

22 Chepter 3














122 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17340 15856 13834 13206 12945 12821

12758 12747 11357 7557 7075 6468 6064 5518 5170 1635 1421 IR (neat) cmndash1

2979 2932

2838 1734 1612 1512 1459 1373 1299 1247 1184 1159 1094 1032 MS (FAB) mz 358 (M+H) +

380 (M+Na) +


3582018 found

3582010














(m 356H) 133ndash118 (m 1115H) 111 (t J = 76 Hz 084 H) 13


50

16816 16636 16551 16455 16405 16302 16273 15888 15856 13824 13766 13612 13528

13398 13306 13096 12955 12945 12878 12832 12827 12809 12767 12757 12751 12726

12660 11377 11329 7416 7161 7135 7080 6563 6221 6195 6167 6118 5517 7167 1732

1663 1393 1385 1370 IR (neat) cmndash1

2981 2936 2905 1738 1652 1513 1457 1372 1250 1205

1177 1096 1067 1030 MS (FAB) mz 556 (M+H)+ 578 (M+Na)



5562547 found 5562547























51







13C-NMR (100 MHz CDCl3) 17382 15864 13832 13180 12947 12821 12747 11365 7634

7091 6465 6065 5522 5147 1657 1431 IR (neat) cmndash1

2979 2933 2837 1730 1611 1513 1460

1372 1302 1247 1185 1108 1033 MS (FAB) mz 358 (M+H) +

380 (M+Na) +



3582018 found 3582023









a colorless oil



oC) 737ndash720 (m


131ndash115 (m 12H) 13

C-NMR (100 MHz CDCl3) 16879 16872 16586 16491 16444 16396

16272 15920 15885 13827 13754 13584 13551 13513 13355 12972 12894 12852 12837

12824 12798 12787 12778 12749 11403 11355 7490 7341 7219 7117 6505 6219 6214

6185 6151 6112 5525 5520 5151 1641 1619 1397 1386 IR (neat) cmndash1

2982 2937 2905

1739 1656 1613 1513 1450 1373 1252 1203 1095 1070 1030 MS (FAB) mz 556 (M+H) +

578


+ found 5562549





52








094 (t J = 74 Hz 3H) 085 (t J = 74 Hz 3H) 13

C-NMR (100 MHz C6D6) 1702 1677 1673 1663

1598 1395 1308 1303 1290 1289 1281 1279 1145 784 716 713 628 625 621 5529

5526 513 465 161 1454 1450 1445 IR (neat) cmndash1

2981 2925 1766 1739 1648 1612 1514

1461 1390 1371 1301 1249 1178 1096 1031 MS (FAB) mz 556 (M+H) +



5562547 found 5562545







C-NMR (100

MHz C6D6) 1707 1671 1667 1651 1593 1387 1312 1300 1285 1283 1277 1276 1138 766

719 716 624 619 616 546 542 505 466 140 139 124 IR (neat) cmndash1

2983 2938 1766 1739

1613 1514 1459 1373 1248 1177 1148 1097 1032 MS (FAB) mz 556 (M+H) +

121 (base peak)


5562547 found 5562549




C-NMR (100

MHz CDCl3) 17035 16717 16663 16632 15871 13750 12961 12854 12832 12772 12766

11357 7216 7007 6893 6202 6187 5606 5520 4872 4588 1547 1403 1399 1396 IR (neat)

cmndash1

2983 2914 2845 1767 1735 1611 1588 1514 1453 1388 1248 1177 1105 1032 MS (FAB)

mz 556 (M+H) +


5562547 found

5562546



53





















54











3033 2359 2306

1737 1677 1610 1585 1537 1516 1486 1394 1322 1248 1179 1117 1061 1033 1006 MS (FAB) mz

1095 (M+Na) +


10949589 found

10949577







Space group C2221


b = 30665(2) Aring = 90deg

c = 134874(12) Aring = 90deg


Z 8



F(000) 4544











55











Space group C2(5)


b = 75202(3) Aring = 1025865(14)deg

c = 236650(9) Aring = 90deg


Z 8



F(000) 2368















56

23 Chapter 4















3560 3092 3010 2924 1706 1673 1627 1573 1440 1410 1346 1290












57






1H




3298 3058 2958 1678 1629 1581 1448 1419 1358




194ndash187 (1H m) 13

C NMR (100 MHz CDCl3) 20910 16553 14294 13841 13754 13634

12973 12914 12858 12767 12711 12640 12437 5337 3368 2522 2142 MS (ESI) mz 390


+ 3901134 found 3901138










3265 3028 2924 1676 1573 1494 1449 1330 1190 1159 1088 1H



245ndash228 (5H m) 13

C NMR (100 MHz CDCl3) 20938 17011 14378 14253 13821 13688 12966

12943 12908 12843 12727 12699 12155 5944 3429 2837 2156 MS (ESI) mz 390 ([M+Na]+)

58






29




30 respectively


3276 1684 1631 1599 1518 1432 1348 1162 1089




(2H m) 205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20885 16645 14728 14557 14346

13728 13533 12935 12922 12736 12703 12552 12378 5275 3364 2545 2144 MS (FAB) mz

435 ([M+Na]+) 413 ([M+H]


+

4350991 found 4350991


3276 2928 1683 1631 1584 1511 1432 1335 1307 1249 1165 1092



59


(1H m) 13

C NMR (100 MHz CDCl3) 20919 16528 15904 14286 13759 13653 13058 12975

12912 12769 12714 12422 11392 5523 5299 3372 2519 2141 MS (FAB) mz 420 ([M+Na]+)



3269 2922 1684 1630 1583 1491 1426 1338 1162 1091 1H NMR





16579 14313 13747 13695 13600 13362 12952 12922 12872 12785 12709 12477 5285

3370 2529 2144 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3272 2921 1684 1630 1428 1338 1162 1092 1H NMR (400 MHz




(1H m) 13

C NMR (100 MHz CDCl3) 20913 16534 14287 13759 13747 13651 13548 12978

12926 12912 12714 12633 12421 5321 3370 2520 2142 2098 MS (ESI) mz 404 ([M+Na]+



3273 2922 1685 1630 1585 1488 1426 1338 1071 1011 1H NMR



60


m) 13

C NMR (100 MHz CDCl3) 20906 16581 14315 13748 13745 13593 13166 12951

12923 12818 12708 12481 12176 5292 3370 2529 2145 MS (FAB) mz 470 ([M+2+Na]+ base


[M+Na]+ 4680245 found 4682045


3271 2923 1687 1630 1585 1425 1328 1163 1121 1068 1018 1H




205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20904 16607 14322 14234 13740 13574

12986 (q J=324 Hz) 12939 12924 12703 12683 12552 (q J=27 Hz) 12506 12385 (q J=2708

Hz) 5310 3368 2535 2137 MS (FAB) mz 458 ([M+Na]+) 436 ([M+H]




3267 1685 1631 1594 1434 1339 1162 1092 1H NMR (400 MHz




C NMR (100 MHz CDCl3) 20900 16598

14315 14039 13741 13579 13450 12985 12948 12923 12788 12705 12660 12489 12462

5290 3368 2532 2143 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3261 1692 1630 1581 1491 1427 1342 1321 1162

61




m) 13

C NMR (100 MHz CDCl3) 20965 16573 14293 13732 13644 13635 13629 13093

13990 12901 12811 12740 12734 12617 12420 5106 3372 2528 2144 1981 MS (FAB) mz

404 ([M+Na]+) 382 ([M+H]


+)

4041296 found 4041296


3265 2925 1698 1677 1575 1522 1442 1346



m) 244 (3H s) 241ndash237 (2H m) 13

C NMR (100 MHz CDCl3) 20879 16906 14755 14539

14435 14204 13663 12977 12970 12805 12716 12403 12280 5878 3433 2834 2156 MS


+ 4350985

found 4350980


3263 2925 1702 1676 1611 1574 1512 1442 1329 1253 1159 1088




C NMR (100 MHz CDCl3) 20939 17019

15960 14381 14266 13687 13026 12972 12942 12828 12731 12116 11446 5895 5527


[M+Na]+ 4201240 found 4201233

62


3262 2923 1677 1575 1491 1441 1333 1160

1090 cm-1





20924 16980 14391 14234 13684 13672 13423 12966 12951 12910 12845 12716 12285

5874 3429 2835 2155 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3265 2924 1698 1677 1574 1442 1332 1188 1160 1089 1043 1H





17021 14375 14261 13839 13688 13528 12976 12966 12940 12729 12689 12128 5922




3262 3022 2871 1698 1677 1575 1488 1441 1404 1333 1160




C NMR (100 MHz CDCl3) 20914 16969

14398 14229 13723 13680 13211 12970 12955 12875 12719 12244 12187 5884 3429




63


3261 2927 1698 1677 1620 1575 1442 1327 1161





20907 16952 14403 14224 14204 13675 13041 (q J=324 Hz) 12965 12753 12715 12586




3259 2927 1700 1677 1574 1439 1334 1160

1089 cm-1





20924 16969 14406 14214 14018 13673 13486 13029 12973 12954 12852 12719 12515

12210 5887 3431 2835 2157 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]

+ base peak) HRMS



3235 2921 1690 1627 1571 1443 1320 1157 1092




C NMR (100 MHz CDCl3) 20943 17053

14368 14268 13730 13602 13575 13119 12955 12893 12835 12708 12642 12166 5563

3440 2841 2151 1875 MS (FAB) mz 404 ([M+Na]+) 382 ([M+H]


64

















65









oC
















66






6








) and α-d-27 (0169 h-1

) were

obtained











) were obtained

67

68

引用文献


2 For reviews see










136 15775ndash15780








13294ndash13297






1996 227ndash228





41 1737ndash1740




Chem 2007 72 5399ndash5402


69




1733ndash1736





Lett 2007 9 101ndash104








2000 2 3883ndash3885





Chem Soc 1984 106 3880ndash3882





2007 72 3326ndash3331




483ndash493








70


Chem 2015 13 8465ndash8469





3666ndash3667







2013 135 8063ndash8070




3576ndash3579















5206ndash5215



ndash5154



71






7187ndash7188



72

73

謝辞





































6













た (eq 2)













7




























8




















9














10

























11












12












た









13









となった














14














15

16

















17












18

















19









20



















21







22

23























24


























25










26









27














28












29





成に優先した





30



















31









はσC-N+











32


33

第五章結論







合成























34

















35

実験の部

36

37
















38


21 Chapter 2

Synthesis of 4














yellow oil




099H) 146 (s 801H) 123 (t 73 Hz 267H) 116 (t 73 Hz 033H) 13


16847 16833 16697 16579 16451 15895 15860 13758 13719 13415 13398 13273 13256

12927 12903 12847 12820 (2 peaks) 12802 12765 12751 12744 12737 11388 11343 8136

7304 6827 6689 6168 6116 6021 5918 5510 5156 2780 1395 1376 MS (FAB) mz 498

(M+H)+ 520 (M+Na)


+ found

4982491


39










136ndash131 (6H m)










colorless oil []D18




Hz 1H) 216 (s 1H) 125 (t 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17308 15864 13786 13173

12947 12827 12756 12750 11368 7310 7106 6080 6031 5518 5133 1422 IR (neat) cmndash1

2934 2906 2864 1736 1611 1513 1458 1368 1300 1248 1185 1102 1034 MS (FAB) mz 344

(M+H) +

366 (M+Na) +


3441862 found

3441860

40




Hz 3H) 102 (s 9H) 13

C-NMR (100 MHz CDCl3) 17339 15859 13555 13552 13308 13189

12998 12933 12764 11368 6517 6193 6071 5520 5115 2666 1919 1425 IR (neat) cmndash1

MS

(FAB) mz 492 (M+H) +


4922570 found

4922570


= -52 (c 1087 CHCl3) 1H-NMR (400 MHz






Hz 51100 H) 13

C-NMR (100 MHz CDCl3) 1684 1649 1644 1628 1591 1377 1358 1334 1292

1285 1284 1283 1282 1278 1276 1275 1140 1135 732 685 621 618 613 586 552 519 140


2983 2937 1741 1655 1514 1449 1370 1251 1207 1069 1029 MS (FAB) mz

542 (M+H) +

564 (M+Na) +


5422390 found

5422394


= -40 (c 0750 CHCl3) 1H-NMR (400



(9H m) 13

C-NMR (100 MHzCDCl3) 16830 16486 16440 16275 15921 13586 13336 12934

12846 12805 11404 11357 9957 6602 6214 6186 6140 5843 5551 5533 5527 5184 1400


2983 2938 2841 1742 1655 1514 1463 1372 1253 1211 1113 1068

1039 IR (neat) cm-1

2983 2938 1742 1655 1514 1463 1372 1253 1211 1113 1068 1039 MS (FAB)

mz 496 (M+H) +


+ 4962183

found 4962182

41


= -47 (c 0597 CHCl3) 1H-NMR (400




(t J = 75 Hz 06H) 13

C-NMR (100 MHz CDCl3) 16849 16478 16449 16280 15911 13590

13559 13550 13296 13271 13264 12984 12979 12921 12831 12773 12770 11409 11385

11356 6255 6211 6176 6128 6007 5526 5159 2676 1907 1394 1388 IR (neat) cmndash1

2958

2933 2857 1739 1656 1514 1466 1426 1370 1252 1205 1178 1111 1069 1030 MS (FAB) mz 690

(M+H)+712 (M+Na)


+ 6903098 found

6903095
















64 Hz 1H) 284 (m 2H) 131ndash128 (m 12H) 13

C-NMR (100 MHz CDCl3) 17365 15879 13165

42

12958 11381 6101 6037 5531 5135 4233 3158 3094 1442 IR (neat) cmndash1

2962 2902 2836

1734 1612 1513 1462 1367 1300 1247 1178 1034 MS (FAB) mz 326 (M+H) +

348 (M+Na)+ 121 (base


3261790 found 3261786















20100 H) 136ndash108 (m 18 H) 13

C-NMR (100 MHz CDCl3) 16896 16881 16567 16548 16430 16426

16277 15941 15888 13613 13568 13426 13367 12964 12925 12879 12717 11399 11359 6215

6195 6186 6148 5987 5527 5266 4299 4285 3076 3065 2798 2764 1399 1391 1380 IR (neat)

cmndash1

2966 2904 2839 1734 1653 1514 1462 1369 1303 1253 1212 1069 1031 MS (FAB) mz 524

(M+H) +

546 (M+Na) +


5242318 found

5242313









λ = 254 nm t=169 min t=232 min []D18


43




C-NMR

(100 MHz CDCl3) 16952 16947 16715 15882 13745 12993 12881 12829 12764 12741

11359 8131 7316 710 6719 6169 5522 5165 4505 3129 2793 1412 IR (neat) cmndash1

2979

2932 2867 1764 1735 1612 1514 1455 1392 1368 1247 1154 1032 MS (FAB) mz 498 (M+H) +

520

(M+Na) +


4982492 found 4982491


t=165 min t=191 min []D18




1H) 271 (d J 78 Hz 2H) 139 (s 3H) 119 (t J 74 Hz 3H) 13


16988 16774 15891 13718 13003 12837 12824 12778 12760 11363 8129 7337 6797 6447

6162 5523 5354 4480 3090 2788 1298 IR (neat) cmndash1

2979 2931 2869 1765 1732 1612 1514

1456 1391 1367 1248 1154 1097 1063 1031 MS (FAB) mz 498 (M+H) +

520 (M+Na) +

121 (base


4982492 found 4982491







2983 2913 2845 1767 1735 1611 1588 1514 1453 1388 1247 1177 1105

1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +


(M+H) +

4362335 found 4362335





2H) 143 (s 9H) 120 (t J 73 Hz 3H) 110 (t J 69 Hz 3H) 13


17003 16786 15895 13006 12829 11360 8126 6803 6678 6443 6156 5528 5350 4478

3092 2795 1489 1400 IR (neat) cmndash1

2976 2931 2873 1762 1734 1613 1514 1461 1390 1369

1292 1244 1152 1113 1064 1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +



4362335 found 4362335

44















086 (t J = 69 Hz 3H) 081 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1696 1672 1668

1649 1594 1381 1303 1294 1285 1283 1278 1277 1139 733 711 667 623 619 616 548

547 501 453 1394 138 2 1382 IR (neat) cmndash1

2983 2935 2869 1766 1739 1612 1514 1456

1392 1369 1301 1249 1176 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +



5422390 found 5422400






J = 73 Hz 3H) 078 (t J = 73 Hz 3H) 070 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1699 1677

1671 1657 1595 1376 1305 1286 1286 1283 12804 12800 1140 7344 6705 6415 6214 6178

6152 5673 5471 4943 4461 1397 1380 1370 IR (neat) cmndash1

2983 2935 2871 1769 1735 1612 1514

1458 1391 1369 1301 1249 1178 1098 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +

121 (base peak)


5422390 found 5422393

45



= -16 (c 0719 CHCl3 96 ee) 1H-NMR (400 MHz




C-NMR (100

MHz CDCl3) 1692 1667 1666 1656 1589 1358 1357 1324 1300 1299 1278 1277 1137

668 633 621 620 617 552 529 492 449 268 192 1394 1380 137 IR (neat) cmndash1

2961

2934 2859 2369 2315 1769 1736 1650 1613 1514 1468 1428 1390 1370 1301 1251 1177 1108

1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


C38H48NO9Si (M+H) +

6903098 found 6903098







(s 9H) 099 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1695 1676 1670 1660 1589 1362

1357 1323 1318 1303 1300 1280 1278 1267 1136 639 6206 6202 614 597 552 483

441 269 190 1396 1392 136 IR (neat) cmndash1

2961 2934 2859 2369 2315 1769 1736 1650 1613

1514 1468 1428 1390 1370 1301 1251 1177 1108 1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


6903098 found 6903098


46












124 (t J = 68 Hz 3H) 114 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1697 1671 1666

1591 1304 1274 1137 655 622 6203 6196 555 553 493 453 427 320 307 139 138 IR

(neat) cmndash1

2966 2937 2868 1770 1734 1613 1514 1464 1389 1368 1301 1248 1178 1095 1033

MS (FAB) mz 524 (M+H) +

546 (M+Na) +


(M+H) +

5242318 found 5242318



= 24 (c 0551 CHCl3 91 ee) 1H-NMR (400 MHz




C-NMR (100 MHz

CDCl3) 1699 1672 1666 1654 1591 1303 1276 1137 643 6219 6219 6212 6198 560

553 485 453 428 303 291 140 138 IR (neat) cmndash1

2969 1769 1738 1613 1514 1464 1389

1369 1301 1248 1178 1034 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


mz 524 (M+H) +

546 (M+Na) +


5242318 found 5242313












47




















13659 13031 12849 12833 12805 12760 12157 12144 11379 8783 8749 7347 6855 6695 5522










b = 120516(8) Aring = 90deg

c = 271658(19) Aring = 90deg


48

Z 4



F(000) 1608















49

22 Chepter 3














122 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17340 15856 13834 13206 12945 12821

12758 12747 11357 7557 7075 6468 6064 5518 5170 1635 1421 IR (neat) cmndash1

2979 2932

2838 1734 1612 1512 1459 1373 1299 1247 1184 1159 1094 1032 MS (FAB) mz 358 (M+H) +

380 (M+Na) +


3582018 found

3582010














(m 356H) 133ndash118 (m 1115H) 111 (t J = 76 Hz 084 H) 13


50

16816 16636 16551 16455 16405 16302 16273 15888 15856 13824 13766 13612 13528

13398 13306 13096 12955 12945 12878 12832 12827 12809 12767 12757 12751 12726

12660 11377 11329 7416 7161 7135 7080 6563 6221 6195 6167 6118 5517 7167 1732

1663 1393 1385 1370 IR (neat) cmndash1

2981 2936 2905 1738 1652 1513 1457 1372 1250 1205

1177 1096 1067 1030 MS (FAB) mz 556 (M+H)+ 578 (M+Na)



5562547 found 5562547























51







13C-NMR (100 MHz CDCl3) 17382 15864 13832 13180 12947 12821 12747 11365 7634

7091 6465 6065 5522 5147 1657 1431 IR (neat) cmndash1

2979 2933 2837 1730 1611 1513 1460

1372 1302 1247 1185 1108 1033 MS (FAB) mz 358 (M+H) +

380 (M+Na) +



3582018 found 3582023









a colorless oil



oC) 737ndash720 (m


131ndash115 (m 12H) 13

C-NMR (100 MHz CDCl3) 16879 16872 16586 16491 16444 16396

16272 15920 15885 13827 13754 13584 13551 13513 13355 12972 12894 12852 12837

12824 12798 12787 12778 12749 11403 11355 7490 7341 7219 7117 6505 6219 6214

6185 6151 6112 5525 5520 5151 1641 1619 1397 1386 IR (neat) cmndash1

2982 2937 2905

1739 1656 1613 1513 1450 1373 1252 1203 1095 1070 1030 MS (FAB) mz 556 (M+H) +

578


+ found 5562549





52








094 (t J = 74 Hz 3H) 085 (t J = 74 Hz 3H) 13

C-NMR (100 MHz C6D6) 1702 1677 1673 1663

1598 1395 1308 1303 1290 1289 1281 1279 1145 784 716 713 628 625 621 5529

5526 513 465 161 1454 1450 1445 IR (neat) cmndash1

2981 2925 1766 1739 1648 1612 1514

1461 1390 1371 1301 1249 1178 1096 1031 MS (FAB) mz 556 (M+H) +



5562547 found 5562545







C-NMR (100

MHz C6D6) 1707 1671 1667 1651 1593 1387 1312 1300 1285 1283 1277 1276 1138 766

719 716 624 619 616 546 542 505 466 140 139 124 IR (neat) cmndash1

2983 2938 1766 1739

1613 1514 1459 1373 1248 1177 1148 1097 1032 MS (FAB) mz 556 (M+H) +

121 (base peak)


5562547 found 5562549




C-NMR (100

MHz CDCl3) 17035 16717 16663 16632 15871 13750 12961 12854 12832 12772 12766

11357 7216 7007 6893 6202 6187 5606 5520 4872 4588 1547 1403 1399 1396 IR (neat)

cmndash1

2983 2914 2845 1767 1735 1611 1588 1514 1453 1388 1248 1177 1105 1032 MS (FAB)

mz 556 (M+H) +


5562547 found

5562546



53





















54











3033 2359 2306

1737 1677 1610 1585 1537 1516 1486 1394 1322 1248 1179 1117 1061 1033 1006 MS (FAB) mz

1095 (M+Na) +


10949589 found

10949577







Space group C2221


b = 30665(2) Aring = 90deg

c = 134874(12) Aring = 90deg


Z 8



F(000) 4544











55











Space group C2(5)


b = 75202(3) Aring = 1025865(14)deg

c = 236650(9) Aring = 90deg


Z 8



F(000) 2368















56

23 Chapter 4















3560 3092 3010 2924 1706 1673 1627 1573 1440 1410 1346 1290












57






1H




3298 3058 2958 1678 1629 1581 1448 1419 1358




194ndash187 (1H m) 13

C NMR (100 MHz CDCl3) 20910 16553 14294 13841 13754 13634

12973 12914 12858 12767 12711 12640 12437 5337 3368 2522 2142 MS (ESI) mz 390


+ 3901134 found 3901138










3265 3028 2924 1676 1573 1494 1449 1330 1190 1159 1088 1H



245ndash228 (5H m) 13

C NMR (100 MHz CDCl3) 20938 17011 14378 14253 13821 13688 12966

12943 12908 12843 12727 12699 12155 5944 3429 2837 2156 MS (ESI) mz 390 ([M+Na]+)

58






29




30 respectively


3276 1684 1631 1599 1518 1432 1348 1162 1089




(2H m) 205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20885 16645 14728 14557 14346

13728 13533 12935 12922 12736 12703 12552 12378 5275 3364 2545 2144 MS (FAB) mz

435 ([M+Na]+) 413 ([M+H]


+

4350991 found 4350991


3276 2928 1683 1631 1584 1511 1432 1335 1307 1249 1165 1092



59


(1H m) 13

C NMR (100 MHz CDCl3) 20919 16528 15904 14286 13759 13653 13058 12975

12912 12769 12714 12422 11392 5523 5299 3372 2519 2141 MS (FAB) mz 420 ([M+Na]+)



3269 2922 1684 1630 1583 1491 1426 1338 1162 1091 1H NMR





16579 14313 13747 13695 13600 13362 12952 12922 12872 12785 12709 12477 5285

3370 2529 2144 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3272 2921 1684 1630 1428 1338 1162 1092 1H NMR (400 MHz




(1H m) 13

C NMR (100 MHz CDCl3) 20913 16534 14287 13759 13747 13651 13548 12978

12926 12912 12714 12633 12421 5321 3370 2520 2142 2098 MS (ESI) mz 404 ([M+Na]+



3273 2922 1685 1630 1585 1488 1426 1338 1071 1011 1H NMR



60


m) 13

C NMR (100 MHz CDCl3) 20906 16581 14315 13748 13745 13593 13166 12951

12923 12818 12708 12481 12176 5292 3370 2529 2145 MS (FAB) mz 470 ([M+2+Na]+ base


[M+Na]+ 4680245 found 4682045


3271 2923 1687 1630 1585 1425 1328 1163 1121 1068 1018 1H




205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20904 16607 14322 14234 13740 13574

12986 (q J=324 Hz) 12939 12924 12703 12683 12552 (q J=27 Hz) 12506 12385 (q J=2708

Hz) 5310 3368 2535 2137 MS (FAB) mz 458 ([M+Na]+) 436 ([M+H]




3267 1685 1631 1594 1434 1339 1162 1092 1H NMR (400 MHz




C NMR (100 MHz CDCl3) 20900 16598

14315 14039 13741 13579 13450 12985 12948 12923 12788 12705 12660 12489 12462

5290 3368 2532 2143 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3261 1692 1630 1581 1491 1427 1342 1321 1162

61




m) 13

C NMR (100 MHz CDCl3) 20965 16573 14293 13732 13644 13635 13629 13093

13990 12901 12811 12740 12734 12617 12420 5106 3372 2528 2144 1981 MS (FAB) mz

404 ([M+Na]+) 382 ([M+H]


+)

4041296 found 4041296


3265 2925 1698 1677 1575 1522 1442 1346



m) 244 (3H s) 241ndash237 (2H m) 13

C NMR (100 MHz CDCl3) 20879 16906 14755 14539

14435 14204 13663 12977 12970 12805 12716 12403 12280 5878 3433 2834 2156 MS


+ 4350985

found 4350980


3263 2925 1702 1676 1611 1574 1512 1442 1329 1253 1159 1088




C NMR (100 MHz CDCl3) 20939 17019

15960 14381 14266 13687 13026 12972 12942 12828 12731 12116 11446 5895 5527


[M+Na]+ 4201240 found 4201233

62


3262 2923 1677 1575 1491 1441 1333 1160

1090 cm-1





20924 16980 14391 14234 13684 13672 13423 12966 12951 12910 12845 12716 12285

5874 3429 2835 2155 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3265 2924 1698 1677 1574 1442 1332 1188 1160 1089 1043 1H





17021 14375 14261 13839 13688 13528 12976 12966 12940 12729 12689 12128 5922




3262 3022 2871 1698 1677 1575 1488 1441 1404 1333 1160




C NMR (100 MHz CDCl3) 20914 16969

14398 14229 13723 13680 13211 12970 12955 12875 12719 12244 12187 5884 3429




63


3261 2927 1698 1677 1620 1575 1442 1327 1161





20907 16952 14403 14224 14204 13675 13041 (q J=324 Hz) 12965 12753 12715 12586




3259 2927 1700 1677 1574 1439 1334 1160

1089 cm-1





20924 16969 14406 14214 14018 13673 13486 13029 12973 12954 12852 12719 12515

12210 5887 3431 2835 2157 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]

+ base peak) HRMS



3235 2921 1690 1627 1571 1443 1320 1157 1092




C NMR (100 MHz CDCl3) 20943 17053

14368 14268 13730 13602 13575 13119 12955 12893 12835 12708 12642 12166 5563

3440 2841 2151 1875 MS (FAB) mz 404 ([M+Na]+) 382 ([M+H]


64

















65









oC
















66






6








) and α-d-27 (0169 h-1

) were

obtained











) were obtained

67

68

引用文献


2 For reviews see










136 15775ndash15780








13294ndash13297






1996 227ndash228





41 1737ndash1740




Chem 2007 72 5399ndash5402


69




1733ndash1736





Lett 2007 9 101ndash104








2000 2 3883ndash3885





Chem Soc 1984 106 3880ndash3882





2007 72 3326ndash3331




483ndash493








70


Chem 2015 13 8465ndash8469





3666ndash3667







2013 135 8063ndash8070




3576ndash3579















5206ndash5215



ndash5154



71






7187ndash7188



72

73

謝辞





































7




























8




















9














10

























11












12












た









13









となった














14














15

16

















17












18

















19









20



















21







22

23























24


























25










26









27














28












29





成に優先した





30



















31









はσC-N+











32


33

第五章結論







合成























34

















35

実験の部

36

37
















38


21 Chapter 2

Synthesis of 4














yellow oil




099H) 146 (s 801H) 123 (t 73 Hz 267H) 116 (t 73 Hz 033H) 13


16847 16833 16697 16579 16451 15895 15860 13758 13719 13415 13398 13273 13256

12927 12903 12847 12820 (2 peaks) 12802 12765 12751 12744 12737 11388 11343 8136

7304 6827 6689 6168 6116 6021 5918 5510 5156 2780 1395 1376 MS (FAB) mz 498

(M+H)+ 520 (M+Na)


+ found

4982491


39










136ndash131 (6H m)










colorless oil []D18




Hz 1H) 216 (s 1H) 125 (t 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17308 15864 13786 13173

12947 12827 12756 12750 11368 7310 7106 6080 6031 5518 5133 1422 IR (neat) cmndash1

2934 2906 2864 1736 1611 1513 1458 1368 1300 1248 1185 1102 1034 MS (FAB) mz 344

(M+H) +

366 (M+Na) +


3441862 found

3441860

40




Hz 3H) 102 (s 9H) 13

C-NMR (100 MHz CDCl3) 17339 15859 13555 13552 13308 13189

12998 12933 12764 11368 6517 6193 6071 5520 5115 2666 1919 1425 IR (neat) cmndash1

MS

(FAB) mz 492 (M+H) +


4922570 found

4922570


= -52 (c 1087 CHCl3) 1H-NMR (400 MHz






Hz 51100 H) 13

C-NMR (100 MHz CDCl3) 1684 1649 1644 1628 1591 1377 1358 1334 1292

1285 1284 1283 1282 1278 1276 1275 1140 1135 732 685 621 618 613 586 552 519 140


2983 2937 1741 1655 1514 1449 1370 1251 1207 1069 1029 MS (FAB) mz

542 (M+H) +

564 (M+Na) +


5422390 found

5422394


= -40 (c 0750 CHCl3) 1H-NMR (400



(9H m) 13

C-NMR (100 MHzCDCl3) 16830 16486 16440 16275 15921 13586 13336 12934

12846 12805 11404 11357 9957 6602 6214 6186 6140 5843 5551 5533 5527 5184 1400


2983 2938 2841 1742 1655 1514 1463 1372 1253 1211 1113 1068

1039 IR (neat) cm-1

2983 2938 1742 1655 1514 1463 1372 1253 1211 1113 1068 1039 MS (FAB)

mz 496 (M+H) +


+ 4962183

found 4962182

41


= -47 (c 0597 CHCl3) 1H-NMR (400




(t J = 75 Hz 06H) 13

C-NMR (100 MHz CDCl3) 16849 16478 16449 16280 15911 13590

13559 13550 13296 13271 13264 12984 12979 12921 12831 12773 12770 11409 11385

11356 6255 6211 6176 6128 6007 5526 5159 2676 1907 1394 1388 IR (neat) cmndash1

2958

2933 2857 1739 1656 1514 1466 1426 1370 1252 1205 1178 1111 1069 1030 MS (FAB) mz 690

(M+H)+712 (M+Na)


+ 6903098 found

6903095
















64 Hz 1H) 284 (m 2H) 131ndash128 (m 12H) 13

C-NMR (100 MHz CDCl3) 17365 15879 13165

42

12958 11381 6101 6037 5531 5135 4233 3158 3094 1442 IR (neat) cmndash1

2962 2902 2836

1734 1612 1513 1462 1367 1300 1247 1178 1034 MS (FAB) mz 326 (M+H) +

348 (M+Na)+ 121 (base


3261790 found 3261786















20100 H) 136ndash108 (m 18 H) 13

C-NMR (100 MHz CDCl3) 16896 16881 16567 16548 16430 16426

16277 15941 15888 13613 13568 13426 13367 12964 12925 12879 12717 11399 11359 6215

6195 6186 6148 5987 5527 5266 4299 4285 3076 3065 2798 2764 1399 1391 1380 IR (neat)

cmndash1

2966 2904 2839 1734 1653 1514 1462 1369 1303 1253 1212 1069 1031 MS (FAB) mz 524

(M+H) +

546 (M+Na) +


5242318 found

5242313









λ = 254 nm t=169 min t=232 min []D18


43




C-NMR

(100 MHz CDCl3) 16952 16947 16715 15882 13745 12993 12881 12829 12764 12741

11359 8131 7316 710 6719 6169 5522 5165 4505 3129 2793 1412 IR (neat) cmndash1

2979

2932 2867 1764 1735 1612 1514 1455 1392 1368 1247 1154 1032 MS (FAB) mz 498 (M+H) +

520

(M+Na) +


4982492 found 4982491


t=165 min t=191 min []D18




1H) 271 (d J 78 Hz 2H) 139 (s 3H) 119 (t J 74 Hz 3H) 13


16988 16774 15891 13718 13003 12837 12824 12778 12760 11363 8129 7337 6797 6447

6162 5523 5354 4480 3090 2788 1298 IR (neat) cmndash1

2979 2931 2869 1765 1732 1612 1514

1456 1391 1367 1248 1154 1097 1063 1031 MS (FAB) mz 498 (M+H) +

520 (M+Na) +

121 (base


4982492 found 4982491







2983 2913 2845 1767 1735 1611 1588 1514 1453 1388 1247 1177 1105

1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +


(M+H) +

4362335 found 4362335





2H) 143 (s 9H) 120 (t J 73 Hz 3H) 110 (t J 69 Hz 3H) 13


17003 16786 15895 13006 12829 11360 8126 6803 6678 6443 6156 5528 5350 4478

3092 2795 1489 1400 IR (neat) cmndash1

2976 2931 2873 1762 1734 1613 1514 1461 1390 1369

1292 1244 1152 1113 1064 1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +



4362335 found 4362335

44















086 (t J = 69 Hz 3H) 081 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1696 1672 1668

1649 1594 1381 1303 1294 1285 1283 1278 1277 1139 733 711 667 623 619 616 548

547 501 453 1394 138 2 1382 IR (neat) cmndash1

2983 2935 2869 1766 1739 1612 1514 1456

1392 1369 1301 1249 1176 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +



5422390 found 5422400






J = 73 Hz 3H) 078 (t J = 73 Hz 3H) 070 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1699 1677

1671 1657 1595 1376 1305 1286 1286 1283 12804 12800 1140 7344 6705 6415 6214 6178

6152 5673 5471 4943 4461 1397 1380 1370 IR (neat) cmndash1

2983 2935 2871 1769 1735 1612 1514

1458 1391 1369 1301 1249 1178 1098 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +

121 (base peak)


5422390 found 5422393

45



= -16 (c 0719 CHCl3 96 ee) 1H-NMR (400 MHz




C-NMR (100

MHz CDCl3) 1692 1667 1666 1656 1589 1358 1357 1324 1300 1299 1278 1277 1137

668 633 621 620 617 552 529 492 449 268 192 1394 1380 137 IR (neat) cmndash1

2961

2934 2859 2369 2315 1769 1736 1650 1613 1514 1468 1428 1390 1370 1301 1251 1177 1108

1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


C38H48NO9Si (M+H) +

6903098 found 6903098







(s 9H) 099 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1695 1676 1670 1660 1589 1362

1357 1323 1318 1303 1300 1280 1278 1267 1136 639 6206 6202 614 597 552 483

441 269 190 1396 1392 136 IR (neat) cmndash1

2961 2934 2859 2369 2315 1769 1736 1650 1613

1514 1468 1428 1390 1370 1301 1251 1177 1108 1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


6903098 found 6903098


46












124 (t J = 68 Hz 3H) 114 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1697 1671 1666

1591 1304 1274 1137 655 622 6203 6196 555 553 493 453 427 320 307 139 138 IR

(neat) cmndash1

2966 2937 2868 1770 1734 1613 1514 1464 1389 1368 1301 1248 1178 1095 1033

MS (FAB) mz 524 (M+H) +

546 (M+Na) +


(M+H) +

5242318 found 5242318



= 24 (c 0551 CHCl3 91 ee) 1H-NMR (400 MHz




C-NMR (100 MHz

CDCl3) 1699 1672 1666 1654 1591 1303 1276 1137 643 6219 6219 6212 6198 560

553 485 453 428 303 291 140 138 IR (neat) cmndash1

2969 1769 1738 1613 1514 1464 1389

1369 1301 1248 1178 1034 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


mz 524 (M+H) +

546 (M+Na) +


5242318 found 5242313












47




















13659 13031 12849 12833 12805 12760 12157 12144 11379 8783 8749 7347 6855 6695 5522










b = 120516(8) Aring = 90deg

c = 271658(19) Aring = 90deg


48

Z 4



F(000) 1608















49

22 Chepter 3














122 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17340 15856 13834 13206 12945 12821

12758 12747 11357 7557 7075 6468 6064 5518 5170 1635 1421 IR (neat) cmndash1

2979 2932

2838 1734 1612 1512 1459 1373 1299 1247 1184 1159 1094 1032 MS (FAB) mz 358 (M+H) +

380 (M+Na) +


3582018 found

3582010














(m 356H) 133ndash118 (m 1115H) 111 (t J = 76 Hz 084 H) 13


50

16816 16636 16551 16455 16405 16302 16273 15888 15856 13824 13766 13612 13528

13398 13306 13096 12955 12945 12878 12832 12827 12809 12767 12757 12751 12726

12660 11377 11329 7416 7161 7135 7080 6563 6221 6195 6167 6118 5517 7167 1732

1663 1393 1385 1370 IR (neat) cmndash1

2981 2936 2905 1738 1652 1513 1457 1372 1250 1205

1177 1096 1067 1030 MS (FAB) mz 556 (M+H)+ 578 (M+Na)



5562547 found 5562547























51







13C-NMR (100 MHz CDCl3) 17382 15864 13832 13180 12947 12821 12747 11365 7634

7091 6465 6065 5522 5147 1657 1431 IR (neat) cmndash1

2979 2933 2837 1730 1611 1513 1460

1372 1302 1247 1185 1108 1033 MS (FAB) mz 358 (M+H) +

380 (M+Na) +



3582018 found 3582023









a colorless oil



oC) 737ndash720 (m


131ndash115 (m 12H) 13

C-NMR (100 MHz CDCl3) 16879 16872 16586 16491 16444 16396

16272 15920 15885 13827 13754 13584 13551 13513 13355 12972 12894 12852 12837

12824 12798 12787 12778 12749 11403 11355 7490 7341 7219 7117 6505 6219 6214

6185 6151 6112 5525 5520 5151 1641 1619 1397 1386 IR (neat) cmndash1

2982 2937 2905

1739 1656 1613 1513 1450 1373 1252 1203 1095 1070 1030 MS (FAB) mz 556 (M+H) +

578


+ found 5562549





52








094 (t J = 74 Hz 3H) 085 (t J = 74 Hz 3H) 13

C-NMR (100 MHz C6D6) 1702 1677 1673 1663

1598 1395 1308 1303 1290 1289 1281 1279 1145 784 716 713 628 625 621 5529

5526 513 465 161 1454 1450 1445 IR (neat) cmndash1

2981 2925 1766 1739 1648 1612 1514

1461 1390 1371 1301 1249 1178 1096 1031 MS (FAB) mz 556 (M+H) +



5562547 found 5562545







C-NMR (100

MHz C6D6) 1707 1671 1667 1651 1593 1387 1312 1300 1285 1283 1277 1276 1138 766

719 716 624 619 616 546 542 505 466 140 139 124 IR (neat) cmndash1

2983 2938 1766 1739

1613 1514 1459 1373 1248 1177 1148 1097 1032 MS (FAB) mz 556 (M+H) +

121 (base peak)


5562547 found 5562549




C-NMR (100

MHz CDCl3) 17035 16717 16663 16632 15871 13750 12961 12854 12832 12772 12766

11357 7216 7007 6893 6202 6187 5606 5520 4872 4588 1547 1403 1399 1396 IR (neat)

cmndash1

2983 2914 2845 1767 1735 1611 1588 1514 1453 1388 1248 1177 1105 1032 MS (FAB)

mz 556 (M+H) +


5562547 found

5562546



53





















54











3033 2359 2306

1737 1677 1610 1585 1537 1516 1486 1394 1322 1248 1179 1117 1061 1033 1006 MS (FAB) mz

1095 (M+Na) +


10949589 found

10949577







Space group C2221


b = 30665(2) Aring = 90deg

c = 134874(12) Aring = 90deg


Z 8



F(000) 4544











55











Space group C2(5)


b = 75202(3) Aring = 1025865(14)deg

c = 236650(9) Aring = 90deg


Z 8



F(000) 2368















56

23 Chapter 4















3560 3092 3010 2924 1706 1673 1627 1573 1440 1410 1346 1290












57






1H




3298 3058 2958 1678 1629 1581 1448 1419 1358




194ndash187 (1H m) 13

C NMR (100 MHz CDCl3) 20910 16553 14294 13841 13754 13634

12973 12914 12858 12767 12711 12640 12437 5337 3368 2522 2142 MS (ESI) mz 390


+ 3901134 found 3901138










3265 3028 2924 1676 1573 1494 1449 1330 1190 1159 1088 1H



245ndash228 (5H m) 13

C NMR (100 MHz CDCl3) 20938 17011 14378 14253 13821 13688 12966

12943 12908 12843 12727 12699 12155 5944 3429 2837 2156 MS (ESI) mz 390 ([M+Na]+)

58






29




30 respectively


3276 1684 1631 1599 1518 1432 1348 1162 1089




(2H m) 205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20885 16645 14728 14557 14346

13728 13533 12935 12922 12736 12703 12552 12378 5275 3364 2545 2144 MS (FAB) mz

435 ([M+Na]+) 413 ([M+H]


+

4350991 found 4350991


3276 2928 1683 1631 1584 1511 1432 1335 1307 1249 1165 1092



59


(1H m) 13

C NMR (100 MHz CDCl3) 20919 16528 15904 14286 13759 13653 13058 12975

12912 12769 12714 12422 11392 5523 5299 3372 2519 2141 MS (FAB) mz 420 ([M+Na]+)



3269 2922 1684 1630 1583 1491 1426 1338 1162 1091 1H NMR





16579 14313 13747 13695 13600 13362 12952 12922 12872 12785 12709 12477 5285

3370 2529 2144 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3272 2921 1684 1630 1428 1338 1162 1092 1H NMR (400 MHz




(1H m) 13

C NMR (100 MHz CDCl3) 20913 16534 14287 13759 13747 13651 13548 12978

12926 12912 12714 12633 12421 5321 3370 2520 2142 2098 MS (ESI) mz 404 ([M+Na]+



3273 2922 1685 1630 1585 1488 1426 1338 1071 1011 1H NMR



60


m) 13

C NMR (100 MHz CDCl3) 20906 16581 14315 13748 13745 13593 13166 12951

12923 12818 12708 12481 12176 5292 3370 2529 2145 MS (FAB) mz 470 ([M+2+Na]+ base


[M+Na]+ 4680245 found 4682045


3271 2923 1687 1630 1585 1425 1328 1163 1121 1068 1018 1H




205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20904 16607 14322 14234 13740 13574

12986 (q J=324 Hz) 12939 12924 12703 12683 12552 (q J=27 Hz) 12506 12385 (q J=2708

Hz) 5310 3368 2535 2137 MS (FAB) mz 458 ([M+Na]+) 436 ([M+H]




3267 1685 1631 1594 1434 1339 1162 1092 1H NMR (400 MHz




C NMR (100 MHz CDCl3) 20900 16598

14315 14039 13741 13579 13450 12985 12948 12923 12788 12705 12660 12489 12462

5290 3368 2532 2143 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3261 1692 1630 1581 1491 1427 1342 1321 1162

61




m) 13

C NMR (100 MHz CDCl3) 20965 16573 14293 13732 13644 13635 13629 13093

13990 12901 12811 12740 12734 12617 12420 5106 3372 2528 2144 1981 MS (FAB) mz

404 ([M+Na]+) 382 ([M+H]


+)

4041296 found 4041296


3265 2925 1698 1677 1575 1522 1442 1346



m) 244 (3H s) 241ndash237 (2H m) 13

C NMR (100 MHz CDCl3) 20879 16906 14755 14539

14435 14204 13663 12977 12970 12805 12716 12403 12280 5878 3433 2834 2156 MS


+ 4350985

found 4350980


3263 2925 1702 1676 1611 1574 1512 1442 1329 1253 1159 1088




C NMR (100 MHz CDCl3) 20939 17019

15960 14381 14266 13687 13026 12972 12942 12828 12731 12116 11446 5895 5527


[M+Na]+ 4201240 found 4201233

62


3262 2923 1677 1575 1491 1441 1333 1160

1090 cm-1





20924 16980 14391 14234 13684 13672 13423 12966 12951 12910 12845 12716 12285

5874 3429 2835 2155 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3265 2924 1698 1677 1574 1442 1332 1188 1160 1089 1043 1H





17021 14375 14261 13839 13688 13528 12976 12966 12940 12729 12689 12128 5922




3262 3022 2871 1698 1677 1575 1488 1441 1404 1333 1160




C NMR (100 MHz CDCl3) 20914 16969

14398 14229 13723 13680 13211 12970 12955 12875 12719 12244 12187 5884 3429




63


3261 2927 1698 1677 1620 1575 1442 1327 1161





20907 16952 14403 14224 14204 13675 13041 (q J=324 Hz) 12965 12753 12715 12586




3259 2927 1700 1677 1574 1439 1334 1160

1089 cm-1





20924 16969 14406 14214 14018 13673 13486 13029 12973 12954 12852 12719 12515

12210 5887 3431 2835 2157 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]

+ base peak) HRMS



3235 2921 1690 1627 1571 1443 1320 1157 1092




C NMR (100 MHz CDCl3) 20943 17053

14368 14268 13730 13602 13575 13119 12955 12893 12835 12708 12642 12166 5563

3440 2841 2151 1875 MS (FAB) mz 404 ([M+Na]+) 382 ([M+H]


64

















65









oC
















66






6








) and α-d-27 (0169 h-1

) were

obtained











) were obtained

67

68

引用文献


2 For reviews see










136 15775ndash15780








13294ndash13297






1996 227ndash228





41 1737ndash1740




Chem 2007 72 5399ndash5402


69




1733ndash1736





Lett 2007 9 101ndash104








2000 2 3883ndash3885





Chem Soc 1984 106 3880ndash3882





2007 72 3326ndash3331




483ndash493








70


Chem 2015 13 8465ndash8469





3666ndash3667







2013 135 8063ndash8070




3576ndash3579















5206ndash5215



ndash5154



71






7187ndash7188



72

73

謝辞





































8




















9














10

























11












12












た









13









となった














14














15

16

















17












18

















19









20



















21







22

23























24


























25










26









27














28












29





成に優先した





30



















31









はσC-N+











32


33

第五章結論







合成























34

















35

実験の部

36

37
















38


21 Chapter 2

Synthesis of 4














yellow oil




099H) 146 (s 801H) 123 (t 73 Hz 267H) 116 (t 73 Hz 033H) 13


16847 16833 16697 16579 16451 15895 15860 13758 13719 13415 13398 13273 13256

12927 12903 12847 12820 (2 peaks) 12802 12765 12751 12744 12737 11388 11343 8136

7304 6827 6689 6168 6116 6021 5918 5510 5156 2780 1395 1376 MS (FAB) mz 498

(M+H)+ 520 (M+Na)


+ found

4982491


39










136ndash131 (6H m)










colorless oil []D18




Hz 1H) 216 (s 1H) 125 (t 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17308 15864 13786 13173

12947 12827 12756 12750 11368 7310 7106 6080 6031 5518 5133 1422 IR (neat) cmndash1

2934 2906 2864 1736 1611 1513 1458 1368 1300 1248 1185 1102 1034 MS (FAB) mz 344

(M+H) +

366 (M+Na) +


3441862 found

3441860

40




Hz 3H) 102 (s 9H) 13

C-NMR (100 MHz CDCl3) 17339 15859 13555 13552 13308 13189

12998 12933 12764 11368 6517 6193 6071 5520 5115 2666 1919 1425 IR (neat) cmndash1

MS

(FAB) mz 492 (M+H) +


4922570 found

4922570


= -52 (c 1087 CHCl3) 1H-NMR (400 MHz






Hz 51100 H) 13

C-NMR (100 MHz CDCl3) 1684 1649 1644 1628 1591 1377 1358 1334 1292

1285 1284 1283 1282 1278 1276 1275 1140 1135 732 685 621 618 613 586 552 519 140


2983 2937 1741 1655 1514 1449 1370 1251 1207 1069 1029 MS (FAB) mz

542 (M+H) +

564 (M+Na) +


5422390 found

5422394


= -40 (c 0750 CHCl3) 1H-NMR (400



(9H m) 13

C-NMR (100 MHzCDCl3) 16830 16486 16440 16275 15921 13586 13336 12934

12846 12805 11404 11357 9957 6602 6214 6186 6140 5843 5551 5533 5527 5184 1400


2983 2938 2841 1742 1655 1514 1463 1372 1253 1211 1113 1068

1039 IR (neat) cm-1

2983 2938 1742 1655 1514 1463 1372 1253 1211 1113 1068 1039 MS (FAB)

mz 496 (M+H) +


+ 4962183

found 4962182

41


= -47 (c 0597 CHCl3) 1H-NMR (400




(t J = 75 Hz 06H) 13

C-NMR (100 MHz CDCl3) 16849 16478 16449 16280 15911 13590

13559 13550 13296 13271 13264 12984 12979 12921 12831 12773 12770 11409 11385

11356 6255 6211 6176 6128 6007 5526 5159 2676 1907 1394 1388 IR (neat) cmndash1

2958

2933 2857 1739 1656 1514 1466 1426 1370 1252 1205 1178 1111 1069 1030 MS (FAB) mz 690

(M+H)+712 (M+Na)


+ 6903098 found

6903095
















64 Hz 1H) 284 (m 2H) 131ndash128 (m 12H) 13

C-NMR (100 MHz CDCl3) 17365 15879 13165

42

12958 11381 6101 6037 5531 5135 4233 3158 3094 1442 IR (neat) cmndash1

2962 2902 2836

1734 1612 1513 1462 1367 1300 1247 1178 1034 MS (FAB) mz 326 (M+H) +

348 (M+Na)+ 121 (base


3261790 found 3261786















20100 H) 136ndash108 (m 18 H) 13

C-NMR (100 MHz CDCl3) 16896 16881 16567 16548 16430 16426

16277 15941 15888 13613 13568 13426 13367 12964 12925 12879 12717 11399 11359 6215

6195 6186 6148 5987 5527 5266 4299 4285 3076 3065 2798 2764 1399 1391 1380 IR (neat)

cmndash1

2966 2904 2839 1734 1653 1514 1462 1369 1303 1253 1212 1069 1031 MS (FAB) mz 524

(M+H) +

546 (M+Na) +


5242318 found

5242313









λ = 254 nm t=169 min t=232 min []D18


43




C-NMR

(100 MHz CDCl3) 16952 16947 16715 15882 13745 12993 12881 12829 12764 12741

11359 8131 7316 710 6719 6169 5522 5165 4505 3129 2793 1412 IR (neat) cmndash1

2979

2932 2867 1764 1735 1612 1514 1455 1392 1368 1247 1154 1032 MS (FAB) mz 498 (M+H) +

520

(M+Na) +


4982492 found 4982491


t=165 min t=191 min []D18




1H) 271 (d J 78 Hz 2H) 139 (s 3H) 119 (t J 74 Hz 3H) 13


16988 16774 15891 13718 13003 12837 12824 12778 12760 11363 8129 7337 6797 6447

6162 5523 5354 4480 3090 2788 1298 IR (neat) cmndash1

2979 2931 2869 1765 1732 1612 1514

1456 1391 1367 1248 1154 1097 1063 1031 MS (FAB) mz 498 (M+H) +

520 (M+Na) +

121 (base


4982492 found 4982491







2983 2913 2845 1767 1735 1611 1588 1514 1453 1388 1247 1177 1105

1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +


(M+H) +

4362335 found 4362335





2H) 143 (s 9H) 120 (t J 73 Hz 3H) 110 (t J 69 Hz 3H) 13


17003 16786 15895 13006 12829 11360 8126 6803 6678 6443 6156 5528 5350 4478

3092 2795 1489 1400 IR (neat) cmndash1

2976 2931 2873 1762 1734 1613 1514 1461 1390 1369

1292 1244 1152 1113 1064 1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +



4362335 found 4362335

44















086 (t J = 69 Hz 3H) 081 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1696 1672 1668

1649 1594 1381 1303 1294 1285 1283 1278 1277 1139 733 711 667 623 619 616 548

547 501 453 1394 138 2 1382 IR (neat) cmndash1

2983 2935 2869 1766 1739 1612 1514 1456

1392 1369 1301 1249 1176 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +



5422390 found 5422400






J = 73 Hz 3H) 078 (t J = 73 Hz 3H) 070 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1699 1677

1671 1657 1595 1376 1305 1286 1286 1283 12804 12800 1140 7344 6705 6415 6214 6178

6152 5673 5471 4943 4461 1397 1380 1370 IR (neat) cmndash1

2983 2935 2871 1769 1735 1612 1514

1458 1391 1369 1301 1249 1178 1098 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +

121 (base peak)


5422390 found 5422393

45



= -16 (c 0719 CHCl3 96 ee) 1H-NMR (400 MHz




C-NMR (100

MHz CDCl3) 1692 1667 1666 1656 1589 1358 1357 1324 1300 1299 1278 1277 1137

668 633 621 620 617 552 529 492 449 268 192 1394 1380 137 IR (neat) cmndash1

2961

2934 2859 2369 2315 1769 1736 1650 1613 1514 1468 1428 1390 1370 1301 1251 1177 1108

1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


C38H48NO9Si (M+H) +

6903098 found 6903098







(s 9H) 099 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1695 1676 1670 1660 1589 1362

1357 1323 1318 1303 1300 1280 1278 1267 1136 639 6206 6202 614 597 552 483

441 269 190 1396 1392 136 IR (neat) cmndash1

2961 2934 2859 2369 2315 1769 1736 1650 1613

1514 1468 1428 1390 1370 1301 1251 1177 1108 1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


6903098 found 6903098


46












124 (t J = 68 Hz 3H) 114 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1697 1671 1666

1591 1304 1274 1137 655 622 6203 6196 555 553 493 453 427 320 307 139 138 IR

(neat) cmndash1

2966 2937 2868 1770 1734 1613 1514 1464 1389 1368 1301 1248 1178 1095 1033

MS (FAB) mz 524 (M+H) +

546 (M+Na) +


(M+H) +

5242318 found 5242318



= 24 (c 0551 CHCl3 91 ee) 1H-NMR (400 MHz




C-NMR (100 MHz

CDCl3) 1699 1672 1666 1654 1591 1303 1276 1137 643 6219 6219 6212 6198 560

553 485 453 428 303 291 140 138 IR (neat) cmndash1

2969 1769 1738 1613 1514 1464 1389

1369 1301 1248 1178 1034 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


mz 524 (M+H) +

546 (M+Na) +


5242318 found 5242313












47




















13659 13031 12849 12833 12805 12760 12157 12144 11379 8783 8749 7347 6855 6695 5522










b = 120516(8) Aring = 90deg

c = 271658(19) Aring = 90deg


48

Z 4



F(000) 1608















49

22 Chepter 3














122 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17340 15856 13834 13206 12945 12821

12758 12747 11357 7557 7075 6468 6064 5518 5170 1635 1421 IR (neat) cmndash1

2979 2932

2838 1734 1612 1512 1459 1373 1299 1247 1184 1159 1094 1032 MS (FAB) mz 358 (M+H) +

380 (M+Na) +


3582018 found

3582010














(m 356H) 133ndash118 (m 1115H) 111 (t J = 76 Hz 084 H) 13


50

16816 16636 16551 16455 16405 16302 16273 15888 15856 13824 13766 13612 13528

13398 13306 13096 12955 12945 12878 12832 12827 12809 12767 12757 12751 12726

12660 11377 11329 7416 7161 7135 7080 6563 6221 6195 6167 6118 5517 7167 1732

1663 1393 1385 1370 IR (neat) cmndash1

2981 2936 2905 1738 1652 1513 1457 1372 1250 1205

1177 1096 1067 1030 MS (FAB) mz 556 (M+H)+ 578 (M+Na)



5562547 found 5562547























51







13C-NMR (100 MHz CDCl3) 17382 15864 13832 13180 12947 12821 12747 11365 7634

7091 6465 6065 5522 5147 1657 1431 IR (neat) cmndash1

2979 2933 2837 1730 1611 1513 1460

1372 1302 1247 1185 1108 1033 MS (FAB) mz 358 (M+H) +

380 (M+Na) +



3582018 found 3582023









a colorless oil



oC) 737ndash720 (m


131ndash115 (m 12H) 13

C-NMR (100 MHz CDCl3) 16879 16872 16586 16491 16444 16396

16272 15920 15885 13827 13754 13584 13551 13513 13355 12972 12894 12852 12837

12824 12798 12787 12778 12749 11403 11355 7490 7341 7219 7117 6505 6219 6214

6185 6151 6112 5525 5520 5151 1641 1619 1397 1386 IR (neat) cmndash1

2982 2937 2905

1739 1656 1613 1513 1450 1373 1252 1203 1095 1070 1030 MS (FAB) mz 556 (M+H) +

578


+ found 5562549





52








094 (t J = 74 Hz 3H) 085 (t J = 74 Hz 3H) 13

C-NMR (100 MHz C6D6) 1702 1677 1673 1663

1598 1395 1308 1303 1290 1289 1281 1279 1145 784 716 713 628 625 621 5529

5526 513 465 161 1454 1450 1445 IR (neat) cmndash1

2981 2925 1766 1739 1648 1612 1514

1461 1390 1371 1301 1249 1178 1096 1031 MS (FAB) mz 556 (M+H) +



5562547 found 5562545







C-NMR (100

MHz C6D6) 1707 1671 1667 1651 1593 1387 1312 1300 1285 1283 1277 1276 1138 766

719 716 624 619 616 546 542 505 466 140 139 124 IR (neat) cmndash1

2983 2938 1766 1739

1613 1514 1459 1373 1248 1177 1148 1097 1032 MS (FAB) mz 556 (M+H) +

121 (base peak)


5562547 found 5562549




C-NMR (100

MHz CDCl3) 17035 16717 16663 16632 15871 13750 12961 12854 12832 12772 12766

11357 7216 7007 6893 6202 6187 5606 5520 4872 4588 1547 1403 1399 1396 IR (neat)

cmndash1

2983 2914 2845 1767 1735 1611 1588 1514 1453 1388 1248 1177 1105 1032 MS (FAB)

mz 556 (M+H) +


5562547 found

5562546



53





















54











3033 2359 2306

1737 1677 1610 1585 1537 1516 1486 1394 1322 1248 1179 1117 1061 1033 1006 MS (FAB) mz

1095 (M+Na) +


10949589 found

10949577







Space group C2221


b = 30665(2) Aring = 90deg

c = 134874(12) Aring = 90deg


Z 8



F(000) 4544











55











Space group C2(5)


b = 75202(3) Aring = 1025865(14)deg

c = 236650(9) Aring = 90deg


Z 8



F(000) 2368















56

23 Chapter 4















3560 3092 3010 2924 1706 1673 1627 1573 1440 1410 1346 1290












57






1H




3298 3058 2958 1678 1629 1581 1448 1419 1358




194ndash187 (1H m) 13

C NMR (100 MHz CDCl3) 20910 16553 14294 13841 13754 13634

12973 12914 12858 12767 12711 12640 12437 5337 3368 2522 2142 MS (ESI) mz 390


+ 3901134 found 3901138










3265 3028 2924 1676 1573 1494 1449 1330 1190 1159 1088 1H



245ndash228 (5H m) 13

C NMR (100 MHz CDCl3) 20938 17011 14378 14253 13821 13688 12966

12943 12908 12843 12727 12699 12155 5944 3429 2837 2156 MS (ESI) mz 390 ([M+Na]+)

58






29




30 respectively


3276 1684 1631 1599 1518 1432 1348 1162 1089




(2H m) 205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20885 16645 14728 14557 14346

13728 13533 12935 12922 12736 12703 12552 12378 5275 3364 2545 2144 MS (FAB) mz

435 ([M+Na]+) 413 ([M+H]


+

4350991 found 4350991


3276 2928 1683 1631 1584 1511 1432 1335 1307 1249 1165 1092



59


(1H m) 13

C NMR (100 MHz CDCl3) 20919 16528 15904 14286 13759 13653 13058 12975

12912 12769 12714 12422 11392 5523 5299 3372 2519 2141 MS (FAB) mz 420 ([M+Na]+)



3269 2922 1684 1630 1583 1491 1426 1338 1162 1091 1H NMR





16579 14313 13747 13695 13600 13362 12952 12922 12872 12785 12709 12477 5285

3370 2529 2144 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3272 2921 1684 1630 1428 1338 1162 1092 1H NMR (400 MHz




(1H m) 13

C NMR (100 MHz CDCl3) 20913 16534 14287 13759 13747 13651 13548 12978

12926 12912 12714 12633 12421 5321 3370 2520 2142 2098 MS (ESI) mz 404 ([M+Na]+



3273 2922 1685 1630 1585 1488 1426 1338 1071 1011 1H NMR



60


m) 13

C NMR (100 MHz CDCl3) 20906 16581 14315 13748 13745 13593 13166 12951

12923 12818 12708 12481 12176 5292 3370 2529 2145 MS (FAB) mz 470 ([M+2+Na]+ base


[M+Na]+ 4680245 found 4682045


3271 2923 1687 1630 1585 1425 1328 1163 1121 1068 1018 1H




205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20904 16607 14322 14234 13740 13574

12986 (q J=324 Hz) 12939 12924 12703 12683 12552 (q J=27 Hz) 12506 12385 (q J=2708

Hz) 5310 3368 2535 2137 MS (FAB) mz 458 ([M+Na]+) 436 ([M+H]




3267 1685 1631 1594 1434 1339 1162 1092 1H NMR (400 MHz




C NMR (100 MHz CDCl3) 20900 16598

14315 14039 13741 13579 13450 12985 12948 12923 12788 12705 12660 12489 12462

5290 3368 2532 2143 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3261 1692 1630 1581 1491 1427 1342 1321 1162

61




m) 13

C NMR (100 MHz CDCl3) 20965 16573 14293 13732 13644 13635 13629 13093

13990 12901 12811 12740 12734 12617 12420 5106 3372 2528 2144 1981 MS (FAB) mz

404 ([M+Na]+) 382 ([M+H]


+)

4041296 found 4041296


3265 2925 1698 1677 1575 1522 1442 1346



m) 244 (3H s) 241ndash237 (2H m) 13

C NMR (100 MHz CDCl3) 20879 16906 14755 14539

14435 14204 13663 12977 12970 12805 12716 12403 12280 5878 3433 2834 2156 MS


+ 4350985

found 4350980


3263 2925 1702 1676 1611 1574 1512 1442 1329 1253 1159 1088




C NMR (100 MHz CDCl3) 20939 17019

15960 14381 14266 13687 13026 12972 12942 12828 12731 12116 11446 5895 5527


[M+Na]+ 4201240 found 4201233

62


3262 2923 1677 1575 1491 1441 1333 1160

1090 cm-1





20924 16980 14391 14234 13684 13672 13423 12966 12951 12910 12845 12716 12285

5874 3429 2835 2155 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3265 2924 1698 1677 1574 1442 1332 1188 1160 1089 1043 1H





17021 14375 14261 13839 13688 13528 12976 12966 12940 12729 12689 12128 5922




3262 3022 2871 1698 1677 1575 1488 1441 1404 1333 1160




C NMR (100 MHz CDCl3) 20914 16969

14398 14229 13723 13680 13211 12970 12955 12875 12719 12244 12187 5884 3429




63


3261 2927 1698 1677 1620 1575 1442 1327 1161





20907 16952 14403 14224 14204 13675 13041 (q J=324 Hz) 12965 12753 12715 12586




3259 2927 1700 1677 1574 1439 1334 1160

1089 cm-1





20924 16969 14406 14214 14018 13673 13486 13029 12973 12954 12852 12719 12515

12210 5887 3431 2835 2157 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]

+ base peak) HRMS



3235 2921 1690 1627 1571 1443 1320 1157 1092




C NMR (100 MHz CDCl3) 20943 17053

14368 14268 13730 13602 13575 13119 12955 12893 12835 12708 12642 12166 5563

3440 2841 2151 1875 MS (FAB) mz 404 ([M+Na]+) 382 ([M+H]


64

















65









oC
















66






6








) and α-d-27 (0169 h-1

) were

obtained











) were obtained

67

68

引用文献


2 For reviews see










136 15775ndash15780








13294ndash13297






1996 227ndash228





41 1737ndash1740




Chem 2007 72 5399ndash5402


69




1733ndash1736





Lett 2007 9 101ndash104








2000 2 3883ndash3885





Chem Soc 1984 106 3880ndash3882





2007 72 3326ndash3331




483ndash493








70


Chem 2015 13 8465ndash8469





3666ndash3667







2013 135 8063ndash8070




3576ndash3579















5206ndash5215



ndash5154



71






7187ndash7188



72

73

謝辞





































9














10

























11












12












た









13









となった














14














15

16

















17












18

















19









20



















21







22

23























24


























25










26









27














28












29





成に優先した





30



















31









はσC-N+











32


33

第五章結論







合成























34

















35

実験の部

36

37
















38


21 Chapter 2

Synthesis of 4














yellow oil




099H) 146 (s 801H) 123 (t 73 Hz 267H) 116 (t 73 Hz 033H) 13


16847 16833 16697 16579 16451 15895 15860 13758 13719 13415 13398 13273 13256

12927 12903 12847 12820 (2 peaks) 12802 12765 12751 12744 12737 11388 11343 8136

7304 6827 6689 6168 6116 6021 5918 5510 5156 2780 1395 1376 MS (FAB) mz 498

(M+H)+ 520 (M+Na)


+ found

4982491


39










136ndash131 (6H m)










colorless oil []D18




Hz 1H) 216 (s 1H) 125 (t 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17308 15864 13786 13173

12947 12827 12756 12750 11368 7310 7106 6080 6031 5518 5133 1422 IR (neat) cmndash1

2934 2906 2864 1736 1611 1513 1458 1368 1300 1248 1185 1102 1034 MS (FAB) mz 344

(M+H) +

366 (M+Na) +


3441862 found

3441860

40




Hz 3H) 102 (s 9H) 13

C-NMR (100 MHz CDCl3) 17339 15859 13555 13552 13308 13189

12998 12933 12764 11368 6517 6193 6071 5520 5115 2666 1919 1425 IR (neat) cmndash1

MS

(FAB) mz 492 (M+H) +


4922570 found

4922570


= -52 (c 1087 CHCl3) 1H-NMR (400 MHz






Hz 51100 H) 13

C-NMR (100 MHz CDCl3) 1684 1649 1644 1628 1591 1377 1358 1334 1292

1285 1284 1283 1282 1278 1276 1275 1140 1135 732 685 621 618 613 586 552 519 140


2983 2937 1741 1655 1514 1449 1370 1251 1207 1069 1029 MS (FAB) mz

542 (M+H) +

564 (M+Na) +


5422390 found

5422394


= -40 (c 0750 CHCl3) 1H-NMR (400



(9H m) 13

C-NMR (100 MHzCDCl3) 16830 16486 16440 16275 15921 13586 13336 12934

12846 12805 11404 11357 9957 6602 6214 6186 6140 5843 5551 5533 5527 5184 1400


2983 2938 2841 1742 1655 1514 1463 1372 1253 1211 1113 1068

1039 IR (neat) cm-1

2983 2938 1742 1655 1514 1463 1372 1253 1211 1113 1068 1039 MS (FAB)

mz 496 (M+H) +


+ 4962183

found 4962182

41


= -47 (c 0597 CHCl3) 1H-NMR (400




(t J = 75 Hz 06H) 13

C-NMR (100 MHz CDCl3) 16849 16478 16449 16280 15911 13590

13559 13550 13296 13271 13264 12984 12979 12921 12831 12773 12770 11409 11385

11356 6255 6211 6176 6128 6007 5526 5159 2676 1907 1394 1388 IR (neat) cmndash1

2958

2933 2857 1739 1656 1514 1466 1426 1370 1252 1205 1178 1111 1069 1030 MS (FAB) mz 690

(M+H)+712 (M+Na)


+ 6903098 found

6903095
















64 Hz 1H) 284 (m 2H) 131ndash128 (m 12H) 13

C-NMR (100 MHz CDCl3) 17365 15879 13165

42

12958 11381 6101 6037 5531 5135 4233 3158 3094 1442 IR (neat) cmndash1

2962 2902 2836

1734 1612 1513 1462 1367 1300 1247 1178 1034 MS (FAB) mz 326 (M+H) +

348 (M+Na)+ 121 (base


3261790 found 3261786















20100 H) 136ndash108 (m 18 H) 13

C-NMR (100 MHz CDCl3) 16896 16881 16567 16548 16430 16426

16277 15941 15888 13613 13568 13426 13367 12964 12925 12879 12717 11399 11359 6215

6195 6186 6148 5987 5527 5266 4299 4285 3076 3065 2798 2764 1399 1391 1380 IR (neat)

cmndash1

2966 2904 2839 1734 1653 1514 1462 1369 1303 1253 1212 1069 1031 MS (FAB) mz 524

(M+H) +

546 (M+Na) +


5242318 found

5242313









λ = 254 nm t=169 min t=232 min []D18


43




C-NMR

(100 MHz CDCl3) 16952 16947 16715 15882 13745 12993 12881 12829 12764 12741

11359 8131 7316 710 6719 6169 5522 5165 4505 3129 2793 1412 IR (neat) cmndash1

2979

2932 2867 1764 1735 1612 1514 1455 1392 1368 1247 1154 1032 MS (FAB) mz 498 (M+H) +

520

(M+Na) +


4982492 found 4982491


t=165 min t=191 min []D18




1H) 271 (d J 78 Hz 2H) 139 (s 3H) 119 (t J 74 Hz 3H) 13


16988 16774 15891 13718 13003 12837 12824 12778 12760 11363 8129 7337 6797 6447

6162 5523 5354 4480 3090 2788 1298 IR (neat) cmndash1

2979 2931 2869 1765 1732 1612 1514

1456 1391 1367 1248 1154 1097 1063 1031 MS (FAB) mz 498 (M+H) +

520 (M+Na) +

121 (base


4982492 found 4982491







2983 2913 2845 1767 1735 1611 1588 1514 1453 1388 1247 1177 1105

1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +


(M+H) +

4362335 found 4362335





2H) 143 (s 9H) 120 (t J 73 Hz 3H) 110 (t J 69 Hz 3H) 13


17003 16786 15895 13006 12829 11360 8126 6803 6678 6443 6156 5528 5350 4478

3092 2795 1489 1400 IR (neat) cmndash1

2976 2931 2873 1762 1734 1613 1514 1461 1390 1369

1292 1244 1152 1113 1064 1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +



4362335 found 4362335

44















086 (t J = 69 Hz 3H) 081 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1696 1672 1668

1649 1594 1381 1303 1294 1285 1283 1278 1277 1139 733 711 667 623 619 616 548

547 501 453 1394 138 2 1382 IR (neat) cmndash1

2983 2935 2869 1766 1739 1612 1514 1456

1392 1369 1301 1249 1176 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +



5422390 found 5422400






J = 73 Hz 3H) 078 (t J = 73 Hz 3H) 070 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1699 1677

1671 1657 1595 1376 1305 1286 1286 1283 12804 12800 1140 7344 6705 6415 6214 6178

6152 5673 5471 4943 4461 1397 1380 1370 IR (neat) cmndash1

2983 2935 2871 1769 1735 1612 1514

1458 1391 1369 1301 1249 1178 1098 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +

121 (base peak)


5422390 found 5422393

45



= -16 (c 0719 CHCl3 96 ee) 1H-NMR (400 MHz




C-NMR (100

MHz CDCl3) 1692 1667 1666 1656 1589 1358 1357 1324 1300 1299 1278 1277 1137

668 633 621 620 617 552 529 492 449 268 192 1394 1380 137 IR (neat) cmndash1

2961

2934 2859 2369 2315 1769 1736 1650 1613 1514 1468 1428 1390 1370 1301 1251 1177 1108

1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


C38H48NO9Si (M+H) +

6903098 found 6903098







(s 9H) 099 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1695 1676 1670 1660 1589 1362

1357 1323 1318 1303 1300 1280 1278 1267 1136 639 6206 6202 614 597 552 483

441 269 190 1396 1392 136 IR (neat) cmndash1

2961 2934 2859 2369 2315 1769 1736 1650 1613

1514 1468 1428 1390 1370 1301 1251 1177 1108 1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


6903098 found 6903098


46












124 (t J = 68 Hz 3H) 114 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1697 1671 1666

1591 1304 1274 1137 655 622 6203 6196 555 553 493 453 427 320 307 139 138 IR

(neat) cmndash1

2966 2937 2868 1770 1734 1613 1514 1464 1389 1368 1301 1248 1178 1095 1033

MS (FAB) mz 524 (M+H) +

546 (M+Na) +


(M+H) +

5242318 found 5242318



= 24 (c 0551 CHCl3 91 ee) 1H-NMR (400 MHz




C-NMR (100 MHz

CDCl3) 1699 1672 1666 1654 1591 1303 1276 1137 643 6219 6219 6212 6198 560

553 485 453 428 303 291 140 138 IR (neat) cmndash1

2969 1769 1738 1613 1514 1464 1389

1369 1301 1248 1178 1034 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


mz 524 (M+H) +

546 (M+Na) +


5242318 found 5242313












47




















13659 13031 12849 12833 12805 12760 12157 12144 11379 8783 8749 7347 6855 6695 5522










b = 120516(8) Aring = 90deg

c = 271658(19) Aring = 90deg


48

Z 4



F(000) 1608















49

22 Chepter 3














122 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17340 15856 13834 13206 12945 12821

12758 12747 11357 7557 7075 6468 6064 5518 5170 1635 1421 IR (neat) cmndash1

2979 2932

2838 1734 1612 1512 1459 1373 1299 1247 1184 1159 1094 1032 MS (FAB) mz 358 (M+H) +

380 (M+Na) +


3582018 found

3582010














(m 356H) 133ndash118 (m 1115H) 111 (t J = 76 Hz 084 H) 13


50

16816 16636 16551 16455 16405 16302 16273 15888 15856 13824 13766 13612 13528

13398 13306 13096 12955 12945 12878 12832 12827 12809 12767 12757 12751 12726

12660 11377 11329 7416 7161 7135 7080 6563 6221 6195 6167 6118 5517 7167 1732

1663 1393 1385 1370 IR (neat) cmndash1

2981 2936 2905 1738 1652 1513 1457 1372 1250 1205

1177 1096 1067 1030 MS (FAB) mz 556 (M+H)+ 578 (M+Na)



5562547 found 5562547























51







13C-NMR (100 MHz CDCl3) 17382 15864 13832 13180 12947 12821 12747 11365 7634

7091 6465 6065 5522 5147 1657 1431 IR (neat) cmndash1

2979 2933 2837 1730 1611 1513 1460

1372 1302 1247 1185 1108 1033 MS (FAB) mz 358 (M+H) +

380 (M+Na) +



3582018 found 3582023









a colorless oil



oC) 737ndash720 (m


131ndash115 (m 12H) 13

C-NMR (100 MHz CDCl3) 16879 16872 16586 16491 16444 16396

16272 15920 15885 13827 13754 13584 13551 13513 13355 12972 12894 12852 12837

12824 12798 12787 12778 12749 11403 11355 7490 7341 7219 7117 6505 6219 6214

6185 6151 6112 5525 5520 5151 1641 1619 1397 1386 IR (neat) cmndash1

2982 2937 2905

1739 1656 1613 1513 1450 1373 1252 1203 1095 1070 1030 MS (FAB) mz 556 (M+H) +

578


+ found 5562549





52








094 (t J = 74 Hz 3H) 085 (t J = 74 Hz 3H) 13

C-NMR (100 MHz C6D6) 1702 1677 1673 1663

1598 1395 1308 1303 1290 1289 1281 1279 1145 784 716 713 628 625 621 5529

5526 513 465 161 1454 1450 1445 IR (neat) cmndash1

2981 2925 1766 1739 1648 1612 1514

1461 1390 1371 1301 1249 1178 1096 1031 MS (FAB) mz 556 (M+H) +



5562547 found 5562545







C-NMR (100

MHz C6D6) 1707 1671 1667 1651 1593 1387 1312 1300 1285 1283 1277 1276 1138 766

719 716 624 619 616 546 542 505 466 140 139 124 IR (neat) cmndash1

2983 2938 1766 1739

1613 1514 1459 1373 1248 1177 1148 1097 1032 MS (FAB) mz 556 (M+H) +

121 (base peak)


5562547 found 5562549




C-NMR (100

MHz CDCl3) 17035 16717 16663 16632 15871 13750 12961 12854 12832 12772 12766

11357 7216 7007 6893 6202 6187 5606 5520 4872 4588 1547 1403 1399 1396 IR (neat)

cmndash1

2983 2914 2845 1767 1735 1611 1588 1514 1453 1388 1248 1177 1105 1032 MS (FAB)

mz 556 (M+H) +


5562547 found

5562546



53





















54











3033 2359 2306

1737 1677 1610 1585 1537 1516 1486 1394 1322 1248 1179 1117 1061 1033 1006 MS (FAB) mz

1095 (M+Na) +


10949589 found

10949577







Space group C2221


b = 30665(2) Aring = 90deg

c = 134874(12) Aring = 90deg


Z 8



F(000) 4544











55











Space group C2(5)


b = 75202(3) Aring = 1025865(14)deg

c = 236650(9) Aring = 90deg


Z 8



F(000) 2368















56

23 Chapter 4















3560 3092 3010 2924 1706 1673 1627 1573 1440 1410 1346 1290












57






1H




3298 3058 2958 1678 1629 1581 1448 1419 1358




194ndash187 (1H m) 13

C NMR (100 MHz CDCl3) 20910 16553 14294 13841 13754 13634

12973 12914 12858 12767 12711 12640 12437 5337 3368 2522 2142 MS (ESI) mz 390


+ 3901134 found 3901138










3265 3028 2924 1676 1573 1494 1449 1330 1190 1159 1088 1H



245ndash228 (5H m) 13

C NMR (100 MHz CDCl3) 20938 17011 14378 14253 13821 13688 12966

12943 12908 12843 12727 12699 12155 5944 3429 2837 2156 MS (ESI) mz 390 ([M+Na]+)

58






29




30 respectively


3276 1684 1631 1599 1518 1432 1348 1162 1089




(2H m) 205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20885 16645 14728 14557 14346

13728 13533 12935 12922 12736 12703 12552 12378 5275 3364 2545 2144 MS (FAB) mz

435 ([M+Na]+) 413 ([M+H]


+

4350991 found 4350991


3276 2928 1683 1631 1584 1511 1432 1335 1307 1249 1165 1092



59


(1H m) 13

C NMR (100 MHz CDCl3) 20919 16528 15904 14286 13759 13653 13058 12975

12912 12769 12714 12422 11392 5523 5299 3372 2519 2141 MS (FAB) mz 420 ([M+Na]+)



3269 2922 1684 1630 1583 1491 1426 1338 1162 1091 1H NMR





16579 14313 13747 13695 13600 13362 12952 12922 12872 12785 12709 12477 5285

3370 2529 2144 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3272 2921 1684 1630 1428 1338 1162 1092 1H NMR (400 MHz




(1H m) 13

C NMR (100 MHz CDCl3) 20913 16534 14287 13759 13747 13651 13548 12978

12926 12912 12714 12633 12421 5321 3370 2520 2142 2098 MS (ESI) mz 404 ([M+Na]+



3273 2922 1685 1630 1585 1488 1426 1338 1071 1011 1H NMR



60


m) 13

C NMR (100 MHz CDCl3) 20906 16581 14315 13748 13745 13593 13166 12951

12923 12818 12708 12481 12176 5292 3370 2529 2145 MS (FAB) mz 470 ([M+2+Na]+ base


[M+Na]+ 4680245 found 4682045


3271 2923 1687 1630 1585 1425 1328 1163 1121 1068 1018 1H




205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20904 16607 14322 14234 13740 13574

12986 (q J=324 Hz) 12939 12924 12703 12683 12552 (q J=27 Hz) 12506 12385 (q J=2708

Hz) 5310 3368 2535 2137 MS (FAB) mz 458 ([M+Na]+) 436 ([M+H]




3267 1685 1631 1594 1434 1339 1162 1092 1H NMR (400 MHz




C NMR (100 MHz CDCl3) 20900 16598

14315 14039 13741 13579 13450 12985 12948 12923 12788 12705 12660 12489 12462

5290 3368 2532 2143 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3261 1692 1630 1581 1491 1427 1342 1321 1162

61




m) 13

C NMR (100 MHz CDCl3) 20965 16573 14293 13732 13644 13635 13629 13093

13990 12901 12811 12740 12734 12617 12420 5106 3372 2528 2144 1981 MS (FAB) mz

404 ([M+Na]+) 382 ([M+H]


+)

4041296 found 4041296


3265 2925 1698 1677 1575 1522 1442 1346



m) 244 (3H s) 241ndash237 (2H m) 13

C NMR (100 MHz CDCl3) 20879 16906 14755 14539

14435 14204 13663 12977 12970 12805 12716 12403 12280 5878 3433 2834 2156 MS


+ 4350985

found 4350980


3263 2925 1702 1676 1611 1574 1512 1442 1329 1253 1159 1088




C NMR (100 MHz CDCl3) 20939 17019

15960 14381 14266 13687 13026 12972 12942 12828 12731 12116 11446 5895 5527


[M+Na]+ 4201240 found 4201233

62


3262 2923 1677 1575 1491 1441 1333 1160

1090 cm-1





20924 16980 14391 14234 13684 13672 13423 12966 12951 12910 12845 12716 12285

5874 3429 2835 2155 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3265 2924 1698 1677 1574 1442 1332 1188 1160 1089 1043 1H





17021 14375 14261 13839 13688 13528 12976 12966 12940 12729 12689 12128 5922




3262 3022 2871 1698 1677 1575 1488 1441 1404 1333 1160




C NMR (100 MHz CDCl3) 20914 16969

14398 14229 13723 13680 13211 12970 12955 12875 12719 12244 12187 5884 3429




63


3261 2927 1698 1677 1620 1575 1442 1327 1161





20907 16952 14403 14224 14204 13675 13041 (q J=324 Hz) 12965 12753 12715 12586




3259 2927 1700 1677 1574 1439 1334 1160

1089 cm-1





20924 16969 14406 14214 14018 13673 13486 13029 12973 12954 12852 12719 12515

12210 5887 3431 2835 2157 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]

+ base peak) HRMS



3235 2921 1690 1627 1571 1443 1320 1157 1092




C NMR (100 MHz CDCl3) 20943 17053

14368 14268 13730 13602 13575 13119 12955 12893 12835 12708 12642 12166 5563

3440 2841 2151 1875 MS (FAB) mz 404 ([M+Na]+) 382 ([M+H]


64

















65









oC
















66






6








) and α-d-27 (0169 h-1

) were

obtained











) were obtained

67

68

引用文献


2 For reviews see










136 15775ndash15780








13294ndash13297






1996 227ndash228





41 1737ndash1740




Chem 2007 72 5399ndash5402


69




1733ndash1736





Lett 2007 9 101ndash104








2000 2 3883ndash3885





Chem Soc 1984 106 3880ndash3882





2007 72 3326ndash3331




483ndash493








70


Chem 2015 13 8465ndash8469





3666ndash3667







2013 135 8063ndash8070




3576ndash3579















5206ndash5215



ndash5154



71






7187ndash7188



72

73

謝辞





































10

























11












12












た









13









となった














14














15

16

















17












18

















19









20



















21







22

23























24


























25










26









27














28












29





成に優先した





30



















31









はσC-N+











32


33

第五章結論







合成























34

















35

実験の部

36

37
















38


21 Chapter 2

Synthesis of 4














yellow oil




099H) 146 (s 801H) 123 (t 73 Hz 267H) 116 (t 73 Hz 033H) 13


16847 16833 16697 16579 16451 15895 15860 13758 13719 13415 13398 13273 13256

12927 12903 12847 12820 (2 peaks) 12802 12765 12751 12744 12737 11388 11343 8136

7304 6827 6689 6168 6116 6021 5918 5510 5156 2780 1395 1376 MS (FAB) mz 498

(M+H)+ 520 (M+Na)


+ found

4982491


39










136ndash131 (6H m)










colorless oil []D18




Hz 1H) 216 (s 1H) 125 (t 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17308 15864 13786 13173

12947 12827 12756 12750 11368 7310 7106 6080 6031 5518 5133 1422 IR (neat) cmndash1

2934 2906 2864 1736 1611 1513 1458 1368 1300 1248 1185 1102 1034 MS (FAB) mz 344

(M+H) +

366 (M+Na) +


3441862 found

3441860

40




Hz 3H) 102 (s 9H) 13

C-NMR (100 MHz CDCl3) 17339 15859 13555 13552 13308 13189

12998 12933 12764 11368 6517 6193 6071 5520 5115 2666 1919 1425 IR (neat) cmndash1

MS

(FAB) mz 492 (M+H) +


4922570 found

4922570


= -52 (c 1087 CHCl3) 1H-NMR (400 MHz






Hz 51100 H) 13

C-NMR (100 MHz CDCl3) 1684 1649 1644 1628 1591 1377 1358 1334 1292

1285 1284 1283 1282 1278 1276 1275 1140 1135 732 685 621 618 613 586 552 519 140


2983 2937 1741 1655 1514 1449 1370 1251 1207 1069 1029 MS (FAB) mz

542 (M+H) +

564 (M+Na) +


5422390 found

5422394


= -40 (c 0750 CHCl3) 1H-NMR (400



(9H m) 13

C-NMR (100 MHzCDCl3) 16830 16486 16440 16275 15921 13586 13336 12934

12846 12805 11404 11357 9957 6602 6214 6186 6140 5843 5551 5533 5527 5184 1400


2983 2938 2841 1742 1655 1514 1463 1372 1253 1211 1113 1068

1039 IR (neat) cm-1

2983 2938 1742 1655 1514 1463 1372 1253 1211 1113 1068 1039 MS (FAB)

mz 496 (M+H) +


+ 4962183

found 4962182

41


= -47 (c 0597 CHCl3) 1H-NMR (400




(t J = 75 Hz 06H) 13

C-NMR (100 MHz CDCl3) 16849 16478 16449 16280 15911 13590

13559 13550 13296 13271 13264 12984 12979 12921 12831 12773 12770 11409 11385

11356 6255 6211 6176 6128 6007 5526 5159 2676 1907 1394 1388 IR (neat) cmndash1

2958

2933 2857 1739 1656 1514 1466 1426 1370 1252 1205 1178 1111 1069 1030 MS (FAB) mz 690

(M+H)+712 (M+Na)


+ 6903098 found

6903095
















64 Hz 1H) 284 (m 2H) 131ndash128 (m 12H) 13

C-NMR (100 MHz CDCl3) 17365 15879 13165

42

12958 11381 6101 6037 5531 5135 4233 3158 3094 1442 IR (neat) cmndash1

2962 2902 2836

1734 1612 1513 1462 1367 1300 1247 1178 1034 MS (FAB) mz 326 (M+H) +

348 (M+Na)+ 121 (base


3261790 found 3261786















20100 H) 136ndash108 (m 18 H) 13

C-NMR (100 MHz CDCl3) 16896 16881 16567 16548 16430 16426

16277 15941 15888 13613 13568 13426 13367 12964 12925 12879 12717 11399 11359 6215

6195 6186 6148 5987 5527 5266 4299 4285 3076 3065 2798 2764 1399 1391 1380 IR (neat)

cmndash1

2966 2904 2839 1734 1653 1514 1462 1369 1303 1253 1212 1069 1031 MS (FAB) mz 524

(M+H) +

546 (M+Na) +


5242318 found

5242313









λ = 254 nm t=169 min t=232 min []D18


43




C-NMR

(100 MHz CDCl3) 16952 16947 16715 15882 13745 12993 12881 12829 12764 12741

11359 8131 7316 710 6719 6169 5522 5165 4505 3129 2793 1412 IR (neat) cmndash1

2979

2932 2867 1764 1735 1612 1514 1455 1392 1368 1247 1154 1032 MS (FAB) mz 498 (M+H) +

520

(M+Na) +


4982492 found 4982491


t=165 min t=191 min []D18




1H) 271 (d J 78 Hz 2H) 139 (s 3H) 119 (t J 74 Hz 3H) 13


16988 16774 15891 13718 13003 12837 12824 12778 12760 11363 8129 7337 6797 6447

6162 5523 5354 4480 3090 2788 1298 IR (neat) cmndash1

2979 2931 2869 1765 1732 1612 1514

1456 1391 1367 1248 1154 1097 1063 1031 MS (FAB) mz 498 (M+H) +

520 (M+Na) +

121 (base


4982492 found 4982491







2983 2913 2845 1767 1735 1611 1588 1514 1453 1388 1247 1177 1105

1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +


(M+H) +

4362335 found 4362335





2H) 143 (s 9H) 120 (t J 73 Hz 3H) 110 (t J 69 Hz 3H) 13


17003 16786 15895 13006 12829 11360 8126 6803 6678 6443 6156 5528 5350 4478

3092 2795 1489 1400 IR (neat) cmndash1

2976 2931 2873 1762 1734 1613 1514 1461 1390 1369

1292 1244 1152 1113 1064 1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +



4362335 found 4362335

44















086 (t J = 69 Hz 3H) 081 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1696 1672 1668

1649 1594 1381 1303 1294 1285 1283 1278 1277 1139 733 711 667 623 619 616 548

547 501 453 1394 138 2 1382 IR (neat) cmndash1

2983 2935 2869 1766 1739 1612 1514 1456

1392 1369 1301 1249 1176 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +



5422390 found 5422400






J = 73 Hz 3H) 078 (t J = 73 Hz 3H) 070 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1699 1677

1671 1657 1595 1376 1305 1286 1286 1283 12804 12800 1140 7344 6705 6415 6214 6178

6152 5673 5471 4943 4461 1397 1380 1370 IR (neat) cmndash1

2983 2935 2871 1769 1735 1612 1514

1458 1391 1369 1301 1249 1178 1098 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +

121 (base peak)


5422390 found 5422393

45



= -16 (c 0719 CHCl3 96 ee) 1H-NMR (400 MHz




C-NMR (100

MHz CDCl3) 1692 1667 1666 1656 1589 1358 1357 1324 1300 1299 1278 1277 1137

668 633 621 620 617 552 529 492 449 268 192 1394 1380 137 IR (neat) cmndash1

2961

2934 2859 2369 2315 1769 1736 1650 1613 1514 1468 1428 1390 1370 1301 1251 1177 1108

1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


C38H48NO9Si (M+H) +

6903098 found 6903098







(s 9H) 099 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1695 1676 1670 1660 1589 1362

1357 1323 1318 1303 1300 1280 1278 1267 1136 639 6206 6202 614 597 552 483

441 269 190 1396 1392 136 IR (neat) cmndash1

2961 2934 2859 2369 2315 1769 1736 1650 1613

1514 1468 1428 1390 1370 1301 1251 1177 1108 1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


6903098 found 6903098


46












124 (t J = 68 Hz 3H) 114 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1697 1671 1666

1591 1304 1274 1137 655 622 6203 6196 555 553 493 453 427 320 307 139 138 IR

(neat) cmndash1

2966 2937 2868 1770 1734 1613 1514 1464 1389 1368 1301 1248 1178 1095 1033

MS (FAB) mz 524 (M+H) +

546 (M+Na) +


(M+H) +

5242318 found 5242318



= 24 (c 0551 CHCl3 91 ee) 1H-NMR (400 MHz




C-NMR (100 MHz

CDCl3) 1699 1672 1666 1654 1591 1303 1276 1137 643 6219 6219 6212 6198 560

553 485 453 428 303 291 140 138 IR (neat) cmndash1

2969 1769 1738 1613 1514 1464 1389

1369 1301 1248 1178 1034 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


mz 524 (M+H) +

546 (M+Na) +


5242318 found 5242313












47




















13659 13031 12849 12833 12805 12760 12157 12144 11379 8783 8749 7347 6855 6695 5522










b = 120516(8) Aring = 90deg

c = 271658(19) Aring = 90deg


48

Z 4



F(000) 1608















49

22 Chepter 3














122 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17340 15856 13834 13206 12945 12821

12758 12747 11357 7557 7075 6468 6064 5518 5170 1635 1421 IR (neat) cmndash1

2979 2932

2838 1734 1612 1512 1459 1373 1299 1247 1184 1159 1094 1032 MS (FAB) mz 358 (M+H) +

380 (M+Na) +


3582018 found

3582010














(m 356H) 133ndash118 (m 1115H) 111 (t J = 76 Hz 084 H) 13


50

16816 16636 16551 16455 16405 16302 16273 15888 15856 13824 13766 13612 13528

13398 13306 13096 12955 12945 12878 12832 12827 12809 12767 12757 12751 12726

12660 11377 11329 7416 7161 7135 7080 6563 6221 6195 6167 6118 5517 7167 1732

1663 1393 1385 1370 IR (neat) cmndash1

2981 2936 2905 1738 1652 1513 1457 1372 1250 1205

1177 1096 1067 1030 MS (FAB) mz 556 (M+H)+ 578 (M+Na)



5562547 found 5562547























51







13C-NMR (100 MHz CDCl3) 17382 15864 13832 13180 12947 12821 12747 11365 7634

7091 6465 6065 5522 5147 1657 1431 IR (neat) cmndash1

2979 2933 2837 1730 1611 1513 1460

1372 1302 1247 1185 1108 1033 MS (FAB) mz 358 (M+H) +

380 (M+Na) +



3582018 found 3582023









a colorless oil



oC) 737ndash720 (m


131ndash115 (m 12H) 13

C-NMR (100 MHz CDCl3) 16879 16872 16586 16491 16444 16396

16272 15920 15885 13827 13754 13584 13551 13513 13355 12972 12894 12852 12837

12824 12798 12787 12778 12749 11403 11355 7490 7341 7219 7117 6505 6219 6214

6185 6151 6112 5525 5520 5151 1641 1619 1397 1386 IR (neat) cmndash1

2982 2937 2905

1739 1656 1613 1513 1450 1373 1252 1203 1095 1070 1030 MS (FAB) mz 556 (M+H) +

578


+ found 5562549





52








094 (t J = 74 Hz 3H) 085 (t J = 74 Hz 3H) 13

C-NMR (100 MHz C6D6) 1702 1677 1673 1663

1598 1395 1308 1303 1290 1289 1281 1279 1145 784 716 713 628 625 621 5529

5526 513 465 161 1454 1450 1445 IR (neat) cmndash1

2981 2925 1766 1739 1648 1612 1514

1461 1390 1371 1301 1249 1178 1096 1031 MS (FAB) mz 556 (M+H) +



5562547 found 5562545







C-NMR (100

MHz C6D6) 1707 1671 1667 1651 1593 1387 1312 1300 1285 1283 1277 1276 1138 766

719 716 624 619 616 546 542 505 466 140 139 124 IR (neat) cmndash1

2983 2938 1766 1739

1613 1514 1459 1373 1248 1177 1148 1097 1032 MS (FAB) mz 556 (M+H) +

121 (base peak)


5562547 found 5562549




C-NMR (100

MHz CDCl3) 17035 16717 16663 16632 15871 13750 12961 12854 12832 12772 12766

11357 7216 7007 6893 6202 6187 5606 5520 4872 4588 1547 1403 1399 1396 IR (neat)

cmndash1

2983 2914 2845 1767 1735 1611 1588 1514 1453 1388 1248 1177 1105 1032 MS (FAB)

mz 556 (M+H) +


5562547 found

5562546



53





















54











3033 2359 2306

1737 1677 1610 1585 1537 1516 1486 1394 1322 1248 1179 1117 1061 1033 1006 MS (FAB) mz

1095 (M+Na) +


10949589 found

10949577







Space group C2221


b = 30665(2) Aring = 90deg

c = 134874(12) Aring = 90deg


Z 8



F(000) 4544











55











Space group C2(5)


b = 75202(3) Aring = 1025865(14)deg

c = 236650(9) Aring = 90deg


Z 8



F(000) 2368















56

23 Chapter 4















3560 3092 3010 2924 1706 1673 1627 1573 1440 1410 1346 1290












57






1H




3298 3058 2958 1678 1629 1581 1448 1419 1358




194ndash187 (1H m) 13

C NMR (100 MHz CDCl3) 20910 16553 14294 13841 13754 13634

12973 12914 12858 12767 12711 12640 12437 5337 3368 2522 2142 MS (ESI) mz 390


+ 3901134 found 3901138










3265 3028 2924 1676 1573 1494 1449 1330 1190 1159 1088 1H



245ndash228 (5H m) 13

C NMR (100 MHz CDCl3) 20938 17011 14378 14253 13821 13688 12966

12943 12908 12843 12727 12699 12155 5944 3429 2837 2156 MS (ESI) mz 390 ([M+Na]+)

58






29




30 respectively


3276 1684 1631 1599 1518 1432 1348 1162 1089




(2H m) 205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20885 16645 14728 14557 14346

13728 13533 12935 12922 12736 12703 12552 12378 5275 3364 2545 2144 MS (FAB) mz

435 ([M+Na]+) 413 ([M+H]


+

4350991 found 4350991


3276 2928 1683 1631 1584 1511 1432 1335 1307 1249 1165 1092



59


(1H m) 13

C NMR (100 MHz CDCl3) 20919 16528 15904 14286 13759 13653 13058 12975

12912 12769 12714 12422 11392 5523 5299 3372 2519 2141 MS (FAB) mz 420 ([M+Na]+)



3269 2922 1684 1630 1583 1491 1426 1338 1162 1091 1H NMR





16579 14313 13747 13695 13600 13362 12952 12922 12872 12785 12709 12477 5285

3370 2529 2144 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3272 2921 1684 1630 1428 1338 1162 1092 1H NMR (400 MHz




(1H m) 13

C NMR (100 MHz CDCl3) 20913 16534 14287 13759 13747 13651 13548 12978

12926 12912 12714 12633 12421 5321 3370 2520 2142 2098 MS (ESI) mz 404 ([M+Na]+



3273 2922 1685 1630 1585 1488 1426 1338 1071 1011 1H NMR



60


m) 13

C NMR (100 MHz CDCl3) 20906 16581 14315 13748 13745 13593 13166 12951

12923 12818 12708 12481 12176 5292 3370 2529 2145 MS (FAB) mz 470 ([M+2+Na]+ base


[M+Na]+ 4680245 found 4682045


3271 2923 1687 1630 1585 1425 1328 1163 1121 1068 1018 1H




205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20904 16607 14322 14234 13740 13574

12986 (q J=324 Hz) 12939 12924 12703 12683 12552 (q J=27 Hz) 12506 12385 (q J=2708

Hz) 5310 3368 2535 2137 MS (FAB) mz 458 ([M+Na]+) 436 ([M+H]




3267 1685 1631 1594 1434 1339 1162 1092 1H NMR (400 MHz




C NMR (100 MHz CDCl3) 20900 16598

14315 14039 13741 13579 13450 12985 12948 12923 12788 12705 12660 12489 12462

5290 3368 2532 2143 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3261 1692 1630 1581 1491 1427 1342 1321 1162

61




m) 13

C NMR (100 MHz CDCl3) 20965 16573 14293 13732 13644 13635 13629 13093

13990 12901 12811 12740 12734 12617 12420 5106 3372 2528 2144 1981 MS (FAB) mz

404 ([M+Na]+) 382 ([M+H]


+)

4041296 found 4041296


3265 2925 1698 1677 1575 1522 1442 1346



m) 244 (3H s) 241ndash237 (2H m) 13

C NMR (100 MHz CDCl3) 20879 16906 14755 14539

14435 14204 13663 12977 12970 12805 12716 12403 12280 5878 3433 2834 2156 MS


+ 4350985

found 4350980


3263 2925 1702 1676 1611 1574 1512 1442 1329 1253 1159 1088




C NMR (100 MHz CDCl3) 20939 17019

15960 14381 14266 13687 13026 12972 12942 12828 12731 12116 11446 5895 5527


[M+Na]+ 4201240 found 4201233

62


3262 2923 1677 1575 1491 1441 1333 1160

1090 cm-1





20924 16980 14391 14234 13684 13672 13423 12966 12951 12910 12845 12716 12285

5874 3429 2835 2155 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3265 2924 1698 1677 1574 1442 1332 1188 1160 1089 1043 1H





17021 14375 14261 13839 13688 13528 12976 12966 12940 12729 12689 12128 5922




3262 3022 2871 1698 1677 1575 1488 1441 1404 1333 1160




C NMR (100 MHz CDCl3) 20914 16969

14398 14229 13723 13680 13211 12970 12955 12875 12719 12244 12187 5884 3429




63


3261 2927 1698 1677 1620 1575 1442 1327 1161





20907 16952 14403 14224 14204 13675 13041 (q J=324 Hz) 12965 12753 12715 12586




3259 2927 1700 1677 1574 1439 1334 1160

1089 cm-1





20924 16969 14406 14214 14018 13673 13486 13029 12973 12954 12852 12719 12515

12210 5887 3431 2835 2157 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]

+ base peak) HRMS



3235 2921 1690 1627 1571 1443 1320 1157 1092




C NMR (100 MHz CDCl3) 20943 17053

14368 14268 13730 13602 13575 13119 12955 12893 12835 12708 12642 12166 5563

3440 2841 2151 1875 MS (FAB) mz 404 ([M+Na]+) 382 ([M+H]


64

















65









oC
















66






6








) and α-d-27 (0169 h-1

) were

obtained











) were obtained

67

68

引用文献


2 For reviews see










136 15775ndash15780








13294ndash13297






1996 227ndash228





41 1737ndash1740




Chem 2007 72 5399ndash5402


69




1733ndash1736





Lett 2007 9 101ndash104








2000 2 3883ndash3885





Chem Soc 1984 106 3880ndash3882





2007 72 3326ndash3331




483ndash493








70


Chem 2015 13 8465ndash8469





3666ndash3667







2013 135 8063ndash8070




3576ndash3579















5206ndash5215



ndash5154



71






7187ndash7188



72

73

謝辞





































11












12












た









13









となった














14














15

16

















17












18

















19









20



















21







22

23























24


























25










26









27














28












29





成に優先した





30



















31









はσC-N+











32


33

第五章結論







合成























34

















35

実験の部

36

37
















38


21 Chapter 2

Synthesis of 4














yellow oil




099H) 146 (s 801H) 123 (t 73 Hz 267H) 116 (t 73 Hz 033H) 13


16847 16833 16697 16579 16451 15895 15860 13758 13719 13415 13398 13273 13256

12927 12903 12847 12820 (2 peaks) 12802 12765 12751 12744 12737 11388 11343 8136

7304 6827 6689 6168 6116 6021 5918 5510 5156 2780 1395 1376 MS (FAB) mz 498

(M+H)+ 520 (M+Na)


+ found

4982491


39










136ndash131 (6H m)










colorless oil []D18




Hz 1H) 216 (s 1H) 125 (t 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17308 15864 13786 13173

12947 12827 12756 12750 11368 7310 7106 6080 6031 5518 5133 1422 IR (neat) cmndash1

2934 2906 2864 1736 1611 1513 1458 1368 1300 1248 1185 1102 1034 MS (FAB) mz 344

(M+H) +

366 (M+Na) +


3441862 found

3441860

40




Hz 3H) 102 (s 9H) 13

C-NMR (100 MHz CDCl3) 17339 15859 13555 13552 13308 13189

12998 12933 12764 11368 6517 6193 6071 5520 5115 2666 1919 1425 IR (neat) cmndash1

MS

(FAB) mz 492 (M+H) +


4922570 found

4922570


= -52 (c 1087 CHCl3) 1H-NMR (400 MHz






Hz 51100 H) 13

C-NMR (100 MHz CDCl3) 1684 1649 1644 1628 1591 1377 1358 1334 1292

1285 1284 1283 1282 1278 1276 1275 1140 1135 732 685 621 618 613 586 552 519 140


2983 2937 1741 1655 1514 1449 1370 1251 1207 1069 1029 MS (FAB) mz

542 (M+H) +

564 (M+Na) +


5422390 found

5422394


= -40 (c 0750 CHCl3) 1H-NMR (400



(9H m) 13

C-NMR (100 MHzCDCl3) 16830 16486 16440 16275 15921 13586 13336 12934

12846 12805 11404 11357 9957 6602 6214 6186 6140 5843 5551 5533 5527 5184 1400


2983 2938 2841 1742 1655 1514 1463 1372 1253 1211 1113 1068

1039 IR (neat) cm-1

2983 2938 1742 1655 1514 1463 1372 1253 1211 1113 1068 1039 MS (FAB)

mz 496 (M+H) +


+ 4962183

found 4962182

41


= -47 (c 0597 CHCl3) 1H-NMR (400




(t J = 75 Hz 06H) 13

C-NMR (100 MHz CDCl3) 16849 16478 16449 16280 15911 13590

13559 13550 13296 13271 13264 12984 12979 12921 12831 12773 12770 11409 11385

11356 6255 6211 6176 6128 6007 5526 5159 2676 1907 1394 1388 IR (neat) cmndash1

2958

2933 2857 1739 1656 1514 1466 1426 1370 1252 1205 1178 1111 1069 1030 MS (FAB) mz 690

(M+H)+712 (M+Na)


+ 6903098 found

6903095
















64 Hz 1H) 284 (m 2H) 131ndash128 (m 12H) 13

C-NMR (100 MHz CDCl3) 17365 15879 13165

42

12958 11381 6101 6037 5531 5135 4233 3158 3094 1442 IR (neat) cmndash1

2962 2902 2836

1734 1612 1513 1462 1367 1300 1247 1178 1034 MS (FAB) mz 326 (M+H) +

348 (M+Na)+ 121 (base


3261790 found 3261786















20100 H) 136ndash108 (m 18 H) 13

C-NMR (100 MHz CDCl3) 16896 16881 16567 16548 16430 16426

16277 15941 15888 13613 13568 13426 13367 12964 12925 12879 12717 11399 11359 6215

6195 6186 6148 5987 5527 5266 4299 4285 3076 3065 2798 2764 1399 1391 1380 IR (neat)

cmndash1

2966 2904 2839 1734 1653 1514 1462 1369 1303 1253 1212 1069 1031 MS (FAB) mz 524

(M+H) +

546 (M+Na) +


5242318 found

5242313









λ = 254 nm t=169 min t=232 min []D18


43




C-NMR

(100 MHz CDCl3) 16952 16947 16715 15882 13745 12993 12881 12829 12764 12741

11359 8131 7316 710 6719 6169 5522 5165 4505 3129 2793 1412 IR (neat) cmndash1

2979

2932 2867 1764 1735 1612 1514 1455 1392 1368 1247 1154 1032 MS (FAB) mz 498 (M+H) +

520

(M+Na) +


4982492 found 4982491


t=165 min t=191 min []D18




1H) 271 (d J 78 Hz 2H) 139 (s 3H) 119 (t J 74 Hz 3H) 13


16988 16774 15891 13718 13003 12837 12824 12778 12760 11363 8129 7337 6797 6447

6162 5523 5354 4480 3090 2788 1298 IR (neat) cmndash1

2979 2931 2869 1765 1732 1612 1514

1456 1391 1367 1248 1154 1097 1063 1031 MS (FAB) mz 498 (M+H) +

520 (M+Na) +

121 (base


4982492 found 4982491







2983 2913 2845 1767 1735 1611 1588 1514 1453 1388 1247 1177 1105

1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +


(M+H) +

4362335 found 4362335





2H) 143 (s 9H) 120 (t J 73 Hz 3H) 110 (t J 69 Hz 3H) 13


17003 16786 15895 13006 12829 11360 8126 6803 6678 6443 6156 5528 5350 4478

3092 2795 1489 1400 IR (neat) cmndash1

2976 2931 2873 1762 1734 1613 1514 1461 1390 1369

1292 1244 1152 1113 1064 1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +



4362335 found 4362335

44















086 (t J = 69 Hz 3H) 081 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1696 1672 1668

1649 1594 1381 1303 1294 1285 1283 1278 1277 1139 733 711 667 623 619 616 548

547 501 453 1394 138 2 1382 IR (neat) cmndash1

2983 2935 2869 1766 1739 1612 1514 1456

1392 1369 1301 1249 1176 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +



5422390 found 5422400






J = 73 Hz 3H) 078 (t J = 73 Hz 3H) 070 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1699 1677

1671 1657 1595 1376 1305 1286 1286 1283 12804 12800 1140 7344 6705 6415 6214 6178

6152 5673 5471 4943 4461 1397 1380 1370 IR (neat) cmndash1

2983 2935 2871 1769 1735 1612 1514

1458 1391 1369 1301 1249 1178 1098 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +

121 (base peak)


5422390 found 5422393

45



= -16 (c 0719 CHCl3 96 ee) 1H-NMR (400 MHz




C-NMR (100

MHz CDCl3) 1692 1667 1666 1656 1589 1358 1357 1324 1300 1299 1278 1277 1137

668 633 621 620 617 552 529 492 449 268 192 1394 1380 137 IR (neat) cmndash1

2961

2934 2859 2369 2315 1769 1736 1650 1613 1514 1468 1428 1390 1370 1301 1251 1177 1108

1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


C38H48NO9Si (M+H) +

6903098 found 6903098







(s 9H) 099 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1695 1676 1670 1660 1589 1362

1357 1323 1318 1303 1300 1280 1278 1267 1136 639 6206 6202 614 597 552 483

441 269 190 1396 1392 136 IR (neat) cmndash1

2961 2934 2859 2369 2315 1769 1736 1650 1613

1514 1468 1428 1390 1370 1301 1251 1177 1108 1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


6903098 found 6903098


46












124 (t J = 68 Hz 3H) 114 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1697 1671 1666

1591 1304 1274 1137 655 622 6203 6196 555 553 493 453 427 320 307 139 138 IR

(neat) cmndash1

2966 2937 2868 1770 1734 1613 1514 1464 1389 1368 1301 1248 1178 1095 1033

MS (FAB) mz 524 (M+H) +

546 (M+Na) +


(M+H) +

5242318 found 5242318



= 24 (c 0551 CHCl3 91 ee) 1H-NMR (400 MHz




C-NMR (100 MHz

CDCl3) 1699 1672 1666 1654 1591 1303 1276 1137 643 6219 6219 6212 6198 560

553 485 453 428 303 291 140 138 IR (neat) cmndash1

2969 1769 1738 1613 1514 1464 1389

1369 1301 1248 1178 1034 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


mz 524 (M+H) +

546 (M+Na) +


5242318 found 5242313












47




















13659 13031 12849 12833 12805 12760 12157 12144 11379 8783 8749 7347 6855 6695 5522










b = 120516(8) Aring = 90deg

c = 271658(19) Aring = 90deg


48

Z 4



F(000) 1608















49

22 Chepter 3














122 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17340 15856 13834 13206 12945 12821

12758 12747 11357 7557 7075 6468 6064 5518 5170 1635 1421 IR (neat) cmndash1

2979 2932

2838 1734 1612 1512 1459 1373 1299 1247 1184 1159 1094 1032 MS (FAB) mz 358 (M+H) +

380 (M+Na) +


3582018 found

3582010














(m 356H) 133ndash118 (m 1115H) 111 (t J = 76 Hz 084 H) 13


50

16816 16636 16551 16455 16405 16302 16273 15888 15856 13824 13766 13612 13528

13398 13306 13096 12955 12945 12878 12832 12827 12809 12767 12757 12751 12726

12660 11377 11329 7416 7161 7135 7080 6563 6221 6195 6167 6118 5517 7167 1732

1663 1393 1385 1370 IR (neat) cmndash1

2981 2936 2905 1738 1652 1513 1457 1372 1250 1205

1177 1096 1067 1030 MS (FAB) mz 556 (M+H)+ 578 (M+Na)



5562547 found 5562547























51







13C-NMR (100 MHz CDCl3) 17382 15864 13832 13180 12947 12821 12747 11365 7634

7091 6465 6065 5522 5147 1657 1431 IR (neat) cmndash1

2979 2933 2837 1730 1611 1513 1460

1372 1302 1247 1185 1108 1033 MS (FAB) mz 358 (M+H) +

380 (M+Na) +



3582018 found 3582023









a colorless oil



oC) 737ndash720 (m


131ndash115 (m 12H) 13

C-NMR (100 MHz CDCl3) 16879 16872 16586 16491 16444 16396

16272 15920 15885 13827 13754 13584 13551 13513 13355 12972 12894 12852 12837

12824 12798 12787 12778 12749 11403 11355 7490 7341 7219 7117 6505 6219 6214

6185 6151 6112 5525 5520 5151 1641 1619 1397 1386 IR (neat) cmndash1

2982 2937 2905

1739 1656 1613 1513 1450 1373 1252 1203 1095 1070 1030 MS (FAB) mz 556 (M+H) +

578


+ found 5562549





52








094 (t J = 74 Hz 3H) 085 (t J = 74 Hz 3H) 13

C-NMR (100 MHz C6D6) 1702 1677 1673 1663

1598 1395 1308 1303 1290 1289 1281 1279 1145 784 716 713 628 625 621 5529

5526 513 465 161 1454 1450 1445 IR (neat) cmndash1

2981 2925 1766 1739 1648 1612 1514

1461 1390 1371 1301 1249 1178 1096 1031 MS (FAB) mz 556 (M+H) +



5562547 found 5562545







C-NMR (100

MHz C6D6) 1707 1671 1667 1651 1593 1387 1312 1300 1285 1283 1277 1276 1138 766

719 716 624 619 616 546 542 505 466 140 139 124 IR (neat) cmndash1

2983 2938 1766 1739

1613 1514 1459 1373 1248 1177 1148 1097 1032 MS (FAB) mz 556 (M+H) +

121 (base peak)


5562547 found 5562549




C-NMR (100

MHz CDCl3) 17035 16717 16663 16632 15871 13750 12961 12854 12832 12772 12766

11357 7216 7007 6893 6202 6187 5606 5520 4872 4588 1547 1403 1399 1396 IR (neat)

cmndash1

2983 2914 2845 1767 1735 1611 1588 1514 1453 1388 1248 1177 1105 1032 MS (FAB)

mz 556 (M+H) +


5562547 found

5562546



53





















54











3033 2359 2306

1737 1677 1610 1585 1537 1516 1486 1394 1322 1248 1179 1117 1061 1033 1006 MS (FAB) mz

1095 (M+Na) +


10949589 found

10949577







Space group C2221


b = 30665(2) Aring = 90deg

c = 134874(12) Aring = 90deg


Z 8



F(000) 4544











55











Space group C2(5)


b = 75202(3) Aring = 1025865(14)deg

c = 236650(9) Aring = 90deg


Z 8



F(000) 2368















56

23 Chapter 4















3560 3092 3010 2924 1706 1673 1627 1573 1440 1410 1346 1290












57






1H




3298 3058 2958 1678 1629 1581 1448 1419 1358




194ndash187 (1H m) 13

C NMR (100 MHz CDCl3) 20910 16553 14294 13841 13754 13634

12973 12914 12858 12767 12711 12640 12437 5337 3368 2522 2142 MS (ESI) mz 390


+ 3901134 found 3901138










3265 3028 2924 1676 1573 1494 1449 1330 1190 1159 1088 1H



245ndash228 (5H m) 13

C NMR (100 MHz CDCl3) 20938 17011 14378 14253 13821 13688 12966

12943 12908 12843 12727 12699 12155 5944 3429 2837 2156 MS (ESI) mz 390 ([M+Na]+)

58






29




30 respectively


3276 1684 1631 1599 1518 1432 1348 1162 1089




(2H m) 205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20885 16645 14728 14557 14346

13728 13533 12935 12922 12736 12703 12552 12378 5275 3364 2545 2144 MS (FAB) mz

435 ([M+Na]+) 413 ([M+H]


+

4350991 found 4350991


3276 2928 1683 1631 1584 1511 1432 1335 1307 1249 1165 1092



59


(1H m) 13

C NMR (100 MHz CDCl3) 20919 16528 15904 14286 13759 13653 13058 12975

12912 12769 12714 12422 11392 5523 5299 3372 2519 2141 MS (FAB) mz 420 ([M+Na]+)



3269 2922 1684 1630 1583 1491 1426 1338 1162 1091 1H NMR





16579 14313 13747 13695 13600 13362 12952 12922 12872 12785 12709 12477 5285

3370 2529 2144 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3272 2921 1684 1630 1428 1338 1162 1092 1H NMR (400 MHz




(1H m) 13

C NMR (100 MHz CDCl3) 20913 16534 14287 13759 13747 13651 13548 12978

12926 12912 12714 12633 12421 5321 3370 2520 2142 2098 MS (ESI) mz 404 ([M+Na]+



3273 2922 1685 1630 1585 1488 1426 1338 1071 1011 1H NMR



60


m) 13

C NMR (100 MHz CDCl3) 20906 16581 14315 13748 13745 13593 13166 12951

12923 12818 12708 12481 12176 5292 3370 2529 2145 MS (FAB) mz 470 ([M+2+Na]+ base


[M+Na]+ 4680245 found 4682045


3271 2923 1687 1630 1585 1425 1328 1163 1121 1068 1018 1H




205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20904 16607 14322 14234 13740 13574

12986 (q J=324 Hz) 12939 12924 12703 12683 12552 (q J=27 Hz) 12506 12385 (q J=2708

Hz) 5310 3368 2535 2137 MS (FAB) mz 458 ([M+Na]+) 436 ([M+H]




3267 1685 1631 1594 1434 1339 1162 1092 1H NMR (400 MHz




C NMR (100 MHz CDCl3) 20900 16598

14315 14039 13741 13579 13450 12985 12948 12923 12788 12705 12660 12489 12462

5290 3368 2532 2143 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3261 1692 1630 1581 1491 1427 1342 1321 1162

61




m) 13

C NMR (100 MHz CDCl3) 20965 16573 14293 13732 13644 13635 13629 13093

13990 12901 12811 12740 12734 12617 12420 5106 3372 2528 2144 1981 MS (FAB) mz

404 ([M+Na]+) 382 ([M+H]


+)

4041296 found 4041296


3265 2925 1698 1677 1575 1522 1442 1346



m) 244 (3H s) 241ndash237 (2H m) 13

C NMR (100 MHz CDCl3) 20879 16906 14755 14539

14435 14204 13663 12977 12970 12805 12716 12403 12280 5878 3433 2834 2156 MS


+ 4350985

found 4350980


3263 2925 1702 1676 1611 1574 1512 1442 1329 1253 1159 1088




C NMR (100 MHz CDCl3) 20939 17019

15960 14381 14266 13687 13026 12972 12942 12828 12731 12116 11446 5895 5527


[M+Na]+ 4201240 found 4201233

62


3262 2923 1677 1575 1491 1441 1333 1160

1090 cm-1





20924 16980 14391 14234 13684 13672 13423 12966 12951 12910 12845 12716 12285

5874 3429 2835 2155 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3265 2924 1698 1677 1574 1442 1332 1188 1160 1089 1043 1H





17021 14375 14261 13839 13688 13528 12976 12966 12940 12729 12689 12128 5922




3262 3022 2871 1698 1677 1575 1488 1441 1404 1333 1160




C NMR (100 MHz CDCl3) 20914 16969

14398 14229 13723 13680 13211 12970 12955 12875 12719 12244 12187 5884 3429




63


3261 2927 1698 1677 1620 1575 1442 1327 1161





20907 16952 14403 14224 14204 13675 13041 (q J=324 Hz) 12965 12753 12715 12586




3259 2927 1700 1677 1574 1439 1334 1160

1089 cm-1





20924 16969 14406 14214 14018 13673 13486 13029 12973 12954 12852 12719 12515

12210 5887 3431 2835 2157 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]

+ base peak) HRMS



3235 2921 1690 1627 1571 1443 1320 1157 1092




C NMR (100 MHz CDCl3) 20943 17053

14368 14268 13730 13602 13575 13119 12955 12893 12835 12708 12642 12166 5563

3440 2841 2151 1875 MS (FAB) mz 404 ([M+Na]+) 382 ([M+H]


64

















65









oC
















66






6








) and α-d-27 (0169 h-1

) were

obtained











) were obtained

67

68

引用文献


2 For reviews see










136 15775ndash15780








13294ndash13297






1996 227ndash228





41 1737ndash1740




Chem 2007 72 5399ndash5402


69




1733ndash1736





Lett 2007 9 101ndash104








2000 2 3883ndash3885





Chem Soc 1984 106 3880ndash3882





2007 72 3326ndash3331




483ndash493








70


Chem 2015 13 8465ndash8469





3666ndash3667







2013 135 8063ndash8070




3576ndash3579















5206ndash5215



ndash5154



71






7187ndash7188



72

73

謝辞





































12












た









13









となった














14














15

16

















17












18

















19









20



















21







22

23























24


























25










26









27














28












29





成に優先した





30



















31









はσC-N+











32


33

第五章結論







合成























34

















35

実験の部

36

37
















38


21 Chapter 2

Synthesis of 4














yellow oil




099H) 146 (s 801H) 123 (t 73 Hz 267H) 116 (t 73 Hz 033H) 13


16847 16833 16697 16579 16451 15895 15860 13758 13719 13415 13398 13273 13256

12927 12903 12847 12820 (2 peaks) 12802 12765 12751 12744 12737 11388 11343 8136

7304 6827 6689 6168 6116 6021 5918 5510 5156 2780 1395 1376 MS (FAB) mz 498

(M+H)+ 520 (M+Na)


+ found

4982491


39










136ndash131 (6H m)










colorless oil []D18




Hz 1H) 216 (s 1H) 125 (t 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17308 15864 13786 13173

12947 12827 12756 12750 11368 7310 7106 6080 6031 5518 5133 1422 IR (neat) cmndash1

2934 2906 2864 1736 1611 1513 1458 1368 1300 1248 1185 1102 1034 MS (FAB) mz 344

(M+H) +

366 (M+Na) +


3441862 found

3441860

40




Hz 3H) 102 (s 9H) 13

C-NMR (100 MHz CDCl3) 17339 15859 13555 13552 13308 13189

12998 12933 12764 11368 6517 6193 6071 5520 5115 2666 1919 1425 IR (neat) cmndash1

MS

(FAB) mz 492 (M+H) +


4922570 found

4922570


= -52 (c 1087 CHCl3) 1H-NMR (400 MHz






Hz 51100 H) 13

C-NMR (100 MHz CDCl3) 1684 1649 1644 1628 1591 1377 1358 1334 1292

1285 1284 1283 1282 1278 1276 1275 1140 1135 732 685 621 618 613 586 552 519 140


2983 2937 1741 1655 1514 1449 1370 1251 1207 1069 1029 MS (FAB) mz

542 (M+H) +

564 (M+Na) +


5422390 found

5422394


= -40 (c 0750 CHCl3) 1H-NMR (400



(9H m) 13

C-NMR (100 MHzCDCl3) 16830 16486 16440 16275 15921 13586 13336 12934

12846 12805 11404 11357 9957 6602 6214 6186 6140 5843 5551 5533 5527 5184 1400


2983 2938 2841 1742 1655 1514 1463 1372 1253 1211 1113 1068

1039 IR (neat) cm-1

2983 2938 1742 1655 1514 1463 1372 1253 1211 1113 1068 1039 MS (FAB)

mz 496 (M+H) +


+ 4962183

found 4962182

41


= -47 (c 0597 CHCl3) 1H-NMR (400




(t J = 75 Hz 06H) 13

C-NMR (100 MHz CDCl3) 16849 16478 16449 16280 15911 13590

13559 13550 13296 13271 13264 12984 12979 12921 12831 12773 12770 11409 11385

11356 6255 6211 6176 6128 6007 5526 5159 2676 1907 1394 1388 IR (neat) cmndash1

2958

2933 2857 1739 1656 1514 1466 1426 1370 1252 1205 1178 1111 1069 1030 MS (FAB) mz 690

(M+H)+712 (M+Na)


+ 6903098 found

6903095
















64 Hz 1H) 284 (m 2H) 131ndash128 (m 12H) 13

C-NMR (100 MHz CDCl3) 17365 15879 13165

42

12958 11381 6101 6037 5531 5135 4233 3158 3094 1442 IR (neat) cmndash1

2962 2902 2836

1734 1612 1513 1462 1367 1300 1247 1178 1034 MS (FAB) mz 326 (M+H) +

348 (M+Na)+ 121 (base


3261790 found 3261786















20100 H) 136ndash108 (m 18 H) 13

C-NMR (100 MHz CDCl3) 16896 16881 16567 16548 16430 16426

16277 15941 15888 13613 13568 13426 13367 12964 12925 12879 12717 11399 11359 6215

6195 6186 6148 5987 5527 5266 4299 4285 3076 3065 2798 2764 1399 1391 1380 IR (neat)

cmndash1

2966 2904 2839 1734 1653 1514 1462 1369 1303 1253 1212 1069 1031 MS (FAB) mz 524

(M+H) +

546 (M+Na) +


5242318 found

5242313









λ = 254 nm t=169 min t=232 min []D18


43




C-NMR

(100 MHz CDCl3) 16952 16947 16715 15882 13745 12993 12881 12829 12764 12741

11359 8131 7316 710 6719 6169 5522 5165 4505 3129 2793 1412 IR (neat) cmndash1

2979

2932 2867 1764 1735 1612 1514 1455 1392 1368 1247 1154 1032 MS (FAB) mz 498 (M+H) +

520

(M+Na) +


4982492 found 4982491


t=165 min t=191 min []D18




1H) 271 (d J 78 Hz 2H) 139 (s 3H) 119 (t J 74 Hz 3H) 13


16988 16774 15891 13718 13003 12837 12824 12778 12760 11363 8129 7337 6797 6447

6162 5523 5354 4480 3090 2788 1298 IR (neat) cmndash1

2979 2931 2869 1765 1732 1612 1514

1456 1391 1367 1248 1154 1097 1063 1031 MS (FAB) mz 498 (M+H) +

520 (M+Na) +

121 (base


4982492 found 4982491







2983 2913 2845 1767 1735 1611 1588 1514 1453 1388 1247 1177 1105

1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +


(M+H) +

4362335 found 4362335





2H) 143 (s 9H) 120 (t J 73 Hz 3H) 110 (t J 69 Hz 3H) 13


17003 16786 15895 13006 12829 11360 8126 6803 6678 6443 6156 5528 5350 4478

3092 2795 1489 1400 IR (neat) cmndash1

2976 2931 2873 1762 1734 1613 1514 1461 1390 1369

1292 1244 1152 1113 1064 1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +



4362335 found 4362335

44















086 (t J = 69 Hz 3H) 081 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1696 1672 1668

1649 1594 1381 1303 1294 1285 1283 1278 1277 1139 733 711 667 623 619 616 548

547 501 453 1394 138 2 1382 IR (neat) cmndash1

2983 2935 2869 1766 1739 1612 1514 1456

1392 1369 1301 1249 1176 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +



5422390 found 5422400






J = 73 Hz 3H) 078 (t J = 73 Hz 3H) 070 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1699 1677

1671 1657 1595 1376 1305 1286 1286 1283 12804 12800 1140 7344 6705 6415 6214 6178

6152 5673 5471 4943 4461 1397 1380 1370 IR (neat) cmndash1

2983 2935 2871 1769 1735 1612 1514

1458 1391 1369 1301 1249 1178 1098 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +

121 (base peak)


5422390 found 5422393

45



= -16 (c 0719 CHCl3 96 ee) 1H-NMR (400 MHz




C-NMR (100

MHz CDCl3) 1692 1667 1666 1656 1589 1358 1357 1324 1300 1299 1278 1277 1137

668 633 621 620 617 552 529 492 449 268 192 1394 1380 137 IR (neat) cmndash1

2961

2934 2859 2369 2315 1769 1736 1650 1613 1514 1468 1428 1390 1370 1301 1251 1177 1108

1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


C38H48NO9Si (M+H) +

6903098 found 6903098







(s 9H) 099 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1695 1676 1670 1660 1589 1362

1357 1323 1318 1303 1300 1280 1278 1267 1136 639 6206 6202 614 597 552 483

441 269 190 1396 1392 136 IR (neat) cmndash1

2961 2934 2859 2369 2315 1769 1736 1650 1613

1514 1468 1428 1390 1370 1301 1251 1177 1108 1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


6903098 found 6903098


46












124 (t J = 68 Hz 3H) 114 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1697 1671 1666

1591 1304 1274 1137 655 622 6203 6196 555 553 493 453 427 320 307 139 138 IR

(neat) cmndash1

2966 2937 2868 1770 1734 1613 1514 1464 1389 1368 1301 1248 1178 1095 1033

MS (FAB) mz 524 (M+H) +

546 (M+Na) +


(M+H) +

5242318 found 5242318



= 24 (c 0551 CHCl3 91 ee) 1H-NMR (400 MHz




C-NMR (100 MHz

CDCl3) 1699 1672 1666 1654 1591 1303 1276 1137 643 6219 6219 6212 6198 560

553 485 453 428 303 291 140 138 IR (neat) cmndash1

2969 1769 1738 1613 1514 1464 1389

1369 1301 1248 1178 1034 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


mz 524 (M+H) +

546 (M+Na) +


5242318 found 5242313












47




















13659 13031 12849 12833 12805 12760 12157 12144 11379 8783 8749 7347 6855 6695 5522










b = 120516(8) Aring = 90deg

c = 271658(19) Aring = 90deg


48

Z 4



F(000) 1608















49

22 Chepter 3














122 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17340 15856 13834 13206 12945 12821

12758 12747 11357 7557 7075 6468 6064 5518 5170 1635 1421 IR (neat) cmndash1

2979 2932

2838 1734 1612 1512 1459 1373 1299 1247 1184 1159 1094 1032 MS (FAB) mz 358 (M+H) +

380 (M+Na) +


3582018 found

3582010














(m 356H) 133ndash118 (m 1115H) 111 (t J = 76 Hz 084 H) 13


50

16816 16636 16551 16455 16405 16302 16273 15888 15856 13824 13766 13612 13528

13398 13306 13096 12955 12945 12878 12832 12827 12809 12767 12757 12751 12726

12660 11377 11329 7416 7161 7135 7080 6563 6221 6195 6167 6118 5517 7167 1732

1663 1393 1385 1370 IR (neat) cmndash1

2981 2936 2905 1738 1652 1513 1457 1372 1250 1205

1177 1096 1067 1030 MS (FAB) mz 556 (M+H)+ 578 (M+Na)



5562547 found 5562547























51







13C-NMR (100 MHz CDCl3) 17382 15864 13832 13180 12947 12821 12747 11365 7634

7091 6465 6065 5522 5147 1657 1431 IR (neat) cmndash1

2979 2933 2837 1730 1611 1513 1460

1372 1302 1247 1185 1108 1033 MS (FAB) mz 358 (M+H) +

380 (M+Na) +



3582018 found 3582023









a colorless oil



oC) 737ndash720 (m


131ndash115 (m 12H) 13

C-NMR (100 MHz CDCl3) 16879 16872 16586 16491 16444 16396

16272 15920 15885 13827 13754 13584 13551 13513 13355 12972 12894 12852 12837

12824 12798 12787 12778 12749 11403 11355 7490 7341 7219 7117 6505 6219 6214

6185 6151 6112 5525 5520 5151 1641 1619 1397 1386 IR (neat) cmndash1

2982 2937 2905

1739 1656 1613 1513 1450 1373 1252 1203 1095 1070 1030 MS (FAB) mz 556 (M+H) +

578


+ found 5562549





52








094 (t J = 74 Hz 3H) 085 (t J = 74 Hz 3H) 13

C-NMR (100 MHz C6D6) 1702 1677 1673 1663

1598 1395 1308 1303 1290 1289 1281 1279 1145 784 716 713 628 625 621 5529

5526 513 465 161 1454 1450 1445 IR (neat) cmndash1

2981 2925 1766 1739 1648 1612 1514

1461 1390 1371 1301 1249 1178 1096 1031 MS (FAB) mz 556 (M+H) +



5562547 found 5562545







C-NMR (100

MHz C6D6) 1707 1671 1667 1651 1593 1387 1312 1300 1285 1283 1277 1276 1138 766

719 716 624 619 616 546 542 505 466 140 139 124 IR (neat) cmndash1

2983 2938 1766 1739

1613 1514 1459 1373 1248 1177 1148 1097 1032 MS (FAB) mz 556 (M+H) +

121 (base peak)


5562547 found 5562549




C-NMR (100

MHz CDCl3) 17035 16717 16663 16632 15871 13750 12961 12854 12832 12772 12766

11357 7216 7007 6893 6202 6187 5606 5520 4872 4588 1547 1403 1399 1396 IR (neat)

cmndash1

2983 2914 2845 1767 1735 1611 1588 1514 1453 1388 1248 1177 1105 1032 MS (FAB)

mz 556 (M+H) +


5562547 found

5562546



53





















54











3033 2359 2306

1737 1677 1610 1585 1537 1516 1486 1394 1322 1248 1179 1117 1061 1033 1006 MS (FAB) mz

1095 (M+Na) +


10949589 found

10949577







Space group C2221


b = 30665(2) Aring = 90deg

c = 134874(12) Aring = 90deg


Z 8



F(000) 4544











55











Space group C2(5)


b = 75202(3) Aring = 1025865(14)deg

c = 236650(9) Aring = 90deg


Z 8



F(000) 2368















56

23 Chapter 4















3560 3092 3010 2924 1706 1673 1627 1573 1440 1410 1346 1290












57






1H




3298 3058 2958 1678 1629 1581 1448 1419 1358




194ndash187 (1H m) 13

C NMR (100 MHz CDCl3) 20910 16553 14294 13841 13754 13634

12973 12914 12858 12767 12711 12640 12437 5337 3368 2522 2142 MS (ESI) mz 390


+ 3901134 found 3901138










3265 3028 2924 1676 1573 1494 1449 1330 1190 1159 1088 1H



245ndash228 (5H m) 13

C NMR (100 MHz CDCl3) 20938 17011 14378 14253 13821 13688 12966

12943 12908 12843 12727 12699 12155 5944 3429 2837 2156 MS (ESI) mz 390 ([M+Na]+)

58






29




30 respectively


3276 1684 1631 1599 1518 1432 1348 1162 1089




(2H m) 205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20885 16645 14728 14557 14346

13728 13533 12935 12922 12736 12703 12552 12378 5275 3364 2545 2144 MS (FAB) mz

435 ([M+Na]+) 413 ([M+H]


+

4350991 found 4350991


3276 2928 1683 1631 1584 1511 1432 1335 1307 1249 1165 1092



59


(1H m) 13

C NMR (100 MHz CDCl3) 20919 16528 15904 14286 13759 13653 13058 12975

12912 12769 12714 12422 11392 5523 5299 3372 2519 2141 MS (FAB) mz 420 ([M+Na]+)



3269 2922 1684 1630 1583 1491 1426 1338 1162 1091 1H NMR





16579 14313 13747 13695 13600 13362 12952 12922 12872 12785 12709 12477 5285

3370 2529 2144 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3272 2921 1684 1630 1428 1338 1162 1092 1H NMR (400 MHz




(1H m) 13

C NMR (100 MHz CDCl3) 20913 16534 14287 13759 13747 13651 13548 12978

12926 12912 12714 12633 12421 5321 3370 2520 2142 2098 MS (ESI) mz 404 ([M+Na]+



3273 2922 1685 1630 1585 1488 1426 1338 1071 1011 1H NMR



60


m) 13

C NMR (100 MHz CDCl3) 20906 16581 14315 13748 13745 13593 13166 12951

12923 12818 12708 12481 12176 5292 3370 2529 2145 MS (FAB) mz 470 ([M+2+Na]+ base


[M+Na]+ 4680245 found 4682045


3271 2923 1687 1630 1585 1425 1328 1163 1121 1068 1018 1H




205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20904 16607 14322 14234 13740 13574

12986 (q J=324 Hz) 12939 12924 12703 12683 12552 (q J=27 Hz) 12506 12385 (q J=2708

Hz) 5310 3368 2535 2137 MS (FAB) mz 458 ([M+Na]+) 436 ([M+H]




3267 1685 1631 1594 1434 1339 1162 1092 1H NMR (400 MHz




C NMR (100 MHz CDCl3) 20900 16598

14315 14039 13741 13579 13450 12985 12948 12923 12788 12705 12660 12489 12462

5290 3368 2532 2143 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3261 1692 1630 1581 1491 1427 1342 1321 1162

61




m) 13

C NMR (100 MHz CDCl3) 20965 16573 14293 13732 13644 13635 13629 13093

13990 12901 12811 12740 12734 12617 12420 5106 3372 2528 2144 1981 MS (FAB) mz

404 ([M+Na]+) 382 ([M+H]


+)

4041296 found 4041296


3265 2925 1698 1677 1575 1522 1442 1346



m) 244 (3H s) 241ndash237 (2H m) 13

C NMR (100 MHz CDCl3) 20879 16906 14755 14539

14435 14204 13663 12977 12970 12805 12716 12403 12280 5878 3433 2834 2156 MS


+ 4350985

found 4350980


3263 2925 1702 1676 1611 1574 1512 1442 1329 1253 1159 1088




C NMR (100 MHz CDCl3) 20939 17019

15960 14381 14266 13687 13026 12972 12942 12828 12731 12116 11446 5895 5527


[M+Na]+ 4201240 found 4201233

62


3262 2923 1677 1575 1491 1441 1333 1160

1090 cm-1





20924 16980 14391 14234 13684 13672 13423 12966 12951 12910 12845 12716 12285

5874 3429 2835 2155 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3265 2924 1698 1677 1574 1442 1332 1188 1160 1089 1043 1H





17021 14375 14261 13839 13688 13528 12976 12966 12940 12729 12689 12128 5922




3262 3022 2871 1698 1677 1575 1488 1441 1404 1333 1160




C NMR (100 MHz CDCl3) 20914 16969

14398 14229 13723 13680 13211 12970 12955 12875 12719 12244 12187 5884 3429




63


3261 2927 1698 1677 1620 1575 1442 1327 1161





20907 16952 14403 14224 14204 13675 13041 (q J=324 Hz) 12965 12753 12715 12586




3259 2927 1700 1677 1574 1439 1334 1160

1089 cm-1





20924 16969 14406 14214 14018 13673 13486 13029 12973 12954 12852 12719 12515

12210 5887 3431 2835 2157 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]

+ base peak) HRMS



3235 2921 1690 1627 1571 1443 1320 1157 1092




C NMR (100 MHz CDCl3) 20943 17053

14368 14268 13730 13602 13575 13119 12955 12893 12835 12708 12642 12166 5563

3440 2841 2151 1875 MS (FAB) mz 404 ([M+Na]+) 382 ([M+H]


64

















65









oC
















66






6








) and α-d-27 (0169 h-1

) were

obtained











) were obtained

67

68

引用文献


2 For reviews see










136 15775ndash15780








13294ndash13297






1996 227ndash228





41 1737ndash1740




Chem 2007 72 5399ndash5402


69




1733ndash1736





Lett 2007 9 101ndash104








2000 2 3883ndash3885





Chem Soc 1984 106 3880ndash3882





2007 72 3326ndash3331




483ndash493








70


Chem 2015 13 8465ndash8469





3666ndash3667







2013 135 8063ndash8070




3576ndash3579















5206ndash5215



ndash5154



71






7187ndash7188



72

73

謝辞





































13









となった














14














15

16

















17












18

















19









20



















21







22

23























24


























25










26









27














28












29





成に優先した





30



















31









はσC-N+











32


33

第五章結論







合成























34

















35

実験の部

36

37
















38


21 Chapter 2

Synthesis of 4














yellow oil




099H) 146 (s 801H) 123 (t 73 Hz 267H) 116 (t 73 Hz 033H) 13


16847 16833 16697 16579 16451 15895 15860 13758 13719 13415 13398 13273 13256

12927 12903 12847 12820 (2 peaks) 12802 12765 12751 12744 12737 11388 11343 8136

7304 6827 6689 6168 6116 6021 5918 5510 5156 2780 1395 1376 MS (FAB) mz 498

(M+H)+ 520 (M+Na)


+ found

4982491


39










136ndash131 (6H m)










colorless oil []D18




Hz 1H) 216 (s 1H) 125 (t 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17308 15864 13786 13173

12947 12827 12756 12750 11368 7310 7106 6080 6031 5518 5133 1422 IR (neat) cmndash1

2934 2906 2864 1736 1611 1513 1458 1368 1300 1248 1185 1102 1034 MS (FAB) mz 344

(M+H) +

366 (M+Na) +


3441862 found

3441860

40




Hz 3H) 102 (s 9H) 13

C-NMR (100 MHz CDCl3) 17339 15859 13555 13552 13308 13189

12998 12933 12764 11368 6517 6193 6071 5520 5115 2666 1919 1425 IR (neat) cmndash1

MS

(FAB) mz 492 (M+H) +


4922570 found

4922570


= -52 (c 1087 CHCl3) 1H-NMR (400 MHz






Hz 51100 H) 13

C-NMR (100 MHz CDCl3) 1684 1649 1644 1628 1591 1377 1358 1334 1292

1285 1284 1283 1282 1278 1276 1275 1140 1135 732 685 621 618 613 586 552 519 140


2983 2937 1741 1655 1514 1449 1370 1251 1207 1069 1029 MS (FAB) mz

542 (M+H) +

564 (M+Na) +


5422390 found

5422394


= -40 (c 0750 CHCl3) 1H-NMR (400



(9H m) 13

C-NMR (100 MHzCDCl3) 16830 16486 16440 16275 15921 13586 13336 12934

12846 12805 11404 11357 9957 6602 6214 6186 6140 5843 5551 5533 5527 5184 1400


2983 2938 2841 1742 1655 1514 1463 1372 1253 1211 1113 1068

1039 IR (neat) cm-1

2983 2938 1742 1655 1514 1463 1372 1253 1211 1113 1068 1039 MS (FAB)

mz 496 (M+H) +


+ 4962183

found 4962182

41


= -47 (c 0597 CHCl3) 1H-NMR (400




(t J = 75 Hz 06H) 13

C-NMR (100 MHz CDCl3) 16849 16478 16449 16280 15911 13590

13559 13550 13296 13271 13264 12984 12979 12921 12831 12773 12770 11409 11385

11356 6255 6211 6176 6128 6007 5526 5159 2676 1907 1394 1388 IR (neat) cmndash1

2958

2933 2857 1739 1656 1514 1466 1426 1370 1252 1205 1178 1111 1069 1030 MS (FAB) mz 690

(M+H)+712 (M+Na)


+ 6903098 found

6903095
















64 Hz 1H) 284 (m 2H) 131ndash128 (m 12H) 13

C-NMR (100 MHz CDCl3) 17365 15879 13165

42

12958 11381 6101 6037 5531 5135 4233 3158 3094 1442 IR (neat) cmndash1

2962 2902 2836

1734 1612 1513 1462 1367 1300 1247 1178 1034 MS (FAB) mz 326 (M+H) +

348 (M+Na)+ 121 (base


3261790 found 3261786















20100 H) 136ndash108 (m 18 H) 13

C-NMR (100 MHz CDCl3) 16896 16881 16567 16548 16430 16426

16277 15941 15888 13613 13568 13426 13367 12964 12925 12879 12717 11399 11359 6215

6195 6186 6148 5987 5527 5266 4299 4285 3076 3065 2798 2764 1399 1391 1380 IR (neat)

cmndash1

2966 2904 2839 1734 1653 1514 1462 1369 1303 1253 1212 1069 1031 MS (FAB) mz 524

(M+H) +

546 (M+Na) +


5242318 found

5242313









λ = 254 nm t=169 min t=232 min []D18


43




C-NMR

(100 MHz CDCl3) 16952 16947 16715 15882 13745 12993 12881 12829 12764 12741

11359 8131 7316 710 6719 6169 5522 5165 4505 3129 2793 1412 IR (neat) cmndash1

2979

2932 2867 1764 1735 1612 1514 1455 1392 1368 1247 1154 1032 MS (FAB) mz 498 (M+H) +

520

(M+Na) +


4982492 found 4982491


t=165 min t=191 min []D18




1H) 271 (d J 78 Hz 2H) 139 (s 3H) 119 (t J 74 Hz 3H) 13


16988 16774 15891 13718 13003 12837 12824 12778 12760 11363 8129 7337 6797 6447

6162 5523 5354 4480 3090 2788 1298 IR (neat) cmndash1

2979 2931 2869 1765 1732 1612 1514

1456 1391 1367 1248 1154 1097 1063 1031 MS (FAB) mz 498 (M+H) +

520 (M+Na) +

121 (base


4982492 found 4982491







2983 2913 2845 1767 1735 1611 1588 1514 1453 1388 1247 1177 1105

1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +


(M+H) +

4362335 found 4362335





2H) 143 (s 9H) 120 (t J 73 Hz 3H) 110 (t J 69 Hz 3H) 13


17003 16786 15895 13006 12829 11360 8126 6803 6678 6443 6156 5528 5350 4478

3092 2795 1489 1400 IR (neat) cmndash1

2976 2931 2873 1762 1734 1613 1514 1461 1390 1369

1292 1244 1152 1113 1064 1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +



4362335 found 4362335

44















086 (t J = 69 Hz 3H) 081 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1696 1672 1668

1649 1594 1381 1303 1294 1285 1283 1278 1277 1139 733 711 667 623 619 616 548

547 501 453 1394 138 2 1382 IR (neat) cmndash1

2983 2935 2869 1766 1739 1612 1514 1456

1392 1369 1301 1249 1176 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +



5422390 found 5422400






J = 73 Hz 3H) 078 (t J = 73 Hz 3H) 070 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1699 1677

1671 1657 1595 1376 1305 1286 1286 1283 12804 12800 1140 7344 6705 6415 6214 6178

6152 5673 5471 4943 4461 1397 1380 1370 IR (neat) cmndash1

2983 2935 2871 1769 1735 1612 1514

1458 1391 1369 1301 1249 1178 1098 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +

121 (base peak)


5422390 found 5422393

45



= -16 (c 0719 CHCl3 96 ee) 1H-NMR (400 MHz




C-NMR (100

MHz CDCl3) 1692 1667 1666 1656 1589 1358 1357 1324 1300 1299 1278 1277 1137

668 633 621 620 617 552 529 492 449 268 192 1394 1380 137 IR (neat) cmndash1

2961

2934 2859 2369 2315 1769 1736 1650 1613 1514 1468 1428 1390 1370 1301 1251 1177 1108

1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


C38H48NO9Si (M+H) +

6903098 found 6903098







(s 9H) 099 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1695 1676 1670 1660 1589 1362

1357 1323 1318 1303 1300 1280 1278 1267 1136 639 6206 6202 614 597 552 483

441 269 190 1396 1392 136 IR (neat) cmndash1

2961 2934 2859 2369 2315 1769 1736 1650 1613

1514 1468 1428 1390 1370 1301 1251 1177 1108 1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


6903098 found 6903098


46












124 (t J = 68 Hz 3H) 114 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1697 1671 1666

1591 1304 1274 1137 655 622 6203 6196 555 553 493 453 427 320 307 139 138 IR

(neat) cmndash1

2966 2937 2868 1770 1734 1613 1514 1464 1389 1368 1301 1248 1178 1095 1033

MS (FAB) mz 524 (M+H) +

546 (M+Na) +


(M+H) +

5242318 found 5242318



= 24 (c 0551 CHCl3 91 ee) 1H-NMR (400 MHz




C-NMR (100 MHz

CDCl3) 1699 1672 1666 1654 1591 1303 1276 1137 643 6219 6219 6212 6198 560

553 485 453 428 303 291 140 138 IR (neat) cmndash1

2969 1769 1738 1613 1514 1464 1389

1369 1301 1248 1178 1034 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


mz 524 (M+H) +

546 (M+Na) +


5242318 found 5242313












47




















13659 13031 12849 12833 12805 12760 12157 12144 11379 8783 8749 7347 6855 6695 5522










b = 120516(8) Aring = 90deg

c = 271658(19) Aring = 90deg


48

Z 4



F(000) 1608















49

22 Chepter 3














122 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17340 15856 13834 13206 12945 12821

12758 12747 11357 7557 7075 6468 6064 5518 5170 1635 1421 IR (neat) cmndash1

2979 2932

2838 1734 1612 1512 1459 1373 1299 1247 1184 1159 1094 1032 MS (FAB) mz 358 (M+H) +

380 (M+Na) +


3582018 found

3582010














(m 356H) 133ndash118 (m 1115H) 111 (t J = 76 Hz 084 H) 13


50

16816 16636 16551 16455 16405 16302 16273 15888 15856 13824 13766 13612 13528

13398 13306 13096 12955 12945 12878 12832 12827 12809 12767 12757 12751 12726

12660 11377 11329 7416 7161 7135 7080 6563 6221 6195 6167 6118 5517 7167 1732

1663 1393 1385 1370 IR (neat) cmndash1

2981 2936 2905 1738 1652 1513 1457 1372 1250 1205

1177 1096 1067 1030 MS (FAB) mz 556 (M+H)+ 578 (M+Na)



5562547 found 5562547























51







13C-NMR (100 MHz CDCl3) 17382 15864 13832 13180 12947 12821 12747 11365 7634

7091 6465 6065 5522 5147 1657 1431 IR (neat) cmndash1

2979 2933 2837 1730 1611 1513 1460

1372 1302 1247 1185 1108 1033 MS (FAB) mz 358 (M+H) +

380 (M+Na) +



3582018 found 3582023









a colorless oil



oC) 737ndash720 (m


131ndash115 (m 12H) 13

C-NMR (100 MHz CDCl3) 16879 16872 16586 16491 16444 16396

16272 15920 15885 13827 13754 13584 13551 13513 13355 12972 12894 12852 12837

12824 12798 12787 12778 12749 11403 11355 7490 7341 7219 7117 6505 6219 6214

6185 6151 6112 5525 5520 5151 1641 1619 1397 1386 IR (neat) cmndash1

2982 2937 2905

1739 1656 1613 1513 1450 1373 1252 1203 1095 1070 1030 MS (FAB) mz 556 (M+H) +

578


+ found 5562549





52








094 (t J = 74 Hz 3H) 085 (t J = 74 Hz 3H) 13

C-NMR (100 MHz C6D6) 1702 1677 1673 1663

1598 1395 1308 1303 1290 1289 1281 1279 1145 784 716 713 628 625 621 5529

5526 513 465 161 1454 1450 1445 IR (neat) cmndash1

2981 2925 1766 1739 1648 1612 1514

1461 1390 1371 1301 1249 1178 1096 1031 MS (FAB) mz 556 (M+H) +



5562547 found 5562545







C-NMR (100

MHz C6D6) 1707 1671 1667 1651 1593 1387 1312 1300 1285 1283 1277 1276 1138 766

719 716 624 619 616 546 542 505 466 140 139 124 IR (neat) cmndash1

2983 2938 1766 1739

1613 1514 1459 1373 1248 1177 1148 1097 1032 MS (FAB) mz 556 (M+H) +

121 (base peak)


5562547 found 5562549




C-NMR (100

MHz CDCl3) 17035 16717 16663 16632 15871 13750 12961 12854 12832 12772 12766

11357 7216 7007 6893 6202 6187 5606 5520 4872 4588 1547 1403 1399 1396 IR (neat)

cmndash1

2983 2914 2845 1767 1735 1611 1588 1514 1453 1388 1248 1177 1105 1032 MS (FAB)

mz 556 (M+H) +


5562547 found

5562546



53





















54











3033 2359 2306

1737 1677 1610 1585 1537 1516 1486 1394 1322 1248 1179 1117 1061 1033 1006 MS (FAB) mz

1095 (M+Na) +


10949589 found

10949577







Space group C2221


b = 30665(2) Aring = 90deg

c = 134874(12) Aring = 90deg


Z 8



F(000) 4544











55











Space group C2(5)


b = 75202(3) Aring = 1025865(14)deg

c = 236650(9) Aring = 90deg


Z 8



F(000) 2368















56

23 Chapter 4















3560 3092 3010 2924 1706 1673 1627 1573 1440 1410 1346 1290












57






1H




3298 3058 2958 1678 1629 1581 1448 1419 1358




194ndash187 (1H m) 13

C NMR (100 MHz CDCl3) 20910 16553 14294 13841 13754 13634

12973 12914 12858 12767 12711 12640 12437 5337 3368 2522 2142 MS (ESI) mz 390


+ 3901134 found 3901138










3265 3028 2924 1676 1573 1494 1449 1330 1190 1159 1088 1H



245ndash228 (5H m) 13

C NMR (100 MHz CDCl3) 20938 17011 14378 14253 13821 13688 12966

12943 12908 12843 12727 12699 12155 5944 3429 2837 2156 MS (ESI) mz 390 ([M+Na]+)

58






29




30 respectively


3276 1684 1631 1599 1518 1432 1348 1162 1089




(2H m) 205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20885 16645 14728 14557 14346

13728 13533 12935 12922 12736 12703 12552 12378 5275 3364 2545 2144 MS (FAB) mz

435 ([M+Na]+) 413 ([M+H]


+

4350991 found 4350991


3276 2928 1683 1631 1584 1511 1432 1335 1307 1249 1165 1092



59


(1H m) 13

C NMR (100 MHz CDCl3) 20919 16528 15904 14286 13759 13653 13058 12975

12912 12769 12714 12422 11392 5523 5299 3372 2519 2141 MS (FAB) mz 420 ([M+Na]+)



3269 2922 1684 1630 1583 1491 1426 1338 1162 1091 1H NMR





16579 14313 13747 13695 13600 13362 12952 12922 12872 12785 12709 12477 5285

3370 2529 2144 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3272 2921 1684 1630 1428 1338 1162 1092 1H NMR (400 MHz




(1H m) 13

C NMR (100 MHz CDCl3) 20913 16534 14287 13759 13747 13651 13548 12978

12926 12912 12714 12633 12421 5321 3370 2520 2142 2098 MS (ESI) mz 404 ([M+Na]+



3273 2922 1685 1630 1585 1488 1426 1338 1071 1011 1H NMR



60


m) 13

C NMR (100 MHz CDCl3) 20906 16581 14315 13748 13745 13593 13166 12951

12923 12818 12708 12481 12176 5292 3370 2529 2145 MS (FAB) mz 470 ([M+2+Na]+ base


[M+Na]+ 4680245 found 4682045


3271 2923 1687 1630 1585 1425 1328 1163 1121 1068 1018 1H




205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20904 16607 14322 14234 13740 13574

12986 (q J=324 Hz) 12939 12924 12703 12683 12552 (q J=27 Hz) 12506 12385 (q J=2708

Hz) 5310 3368 2535 2137 MS (FAB) mz 458 ([M+Na]+) 436 ([M+H]




3267 1685 1631 1594 1434 1339 1162 1092 1H NMR (400 MHz




C NMR (100 MHz CDCl3) 20900 16598

14315 14039 13741 13579 13450 12985 12948 12923 12788 12705 12660 12489 12462

5290 3368 2532 2143 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3261 1692 1630 1581 1491 1427 1342 1321 1162

61




m) 13

C NMR (100 MHz CDCl3) 20965 16573 14293 13732 13644 13635 13629 13093

13990 12901 12811 12740 12734 12617 12420 5106 3372 2528 2144 1981 MS (FAB) mz

404 ([M+Na]+) 382 ([M+H]


+)

4041296 found 4041296


3265 2925 1698 1677 1575 1522 1442 1346



m) 244 (3H s) 241ndash237 (2H m) 13

C NMR (100 MHz CDCl3) 20879 16906 14755 14539

14435 14204 13663 12977 12970 12805 12716 12403 12280 5878 3433 2834 2156 MS


+ 4350985

found 4350980


3263 2925 1702 1676 1611 1574 1512 1442 1329 1253 1159 1088




C NMR (100 MHz CDCl3) 20939 17019

15960 14381 14266 13687 13026 12972 12942 12828 12731 12116 11446 5895 5527


[M+Na]+ 4201240 found 4201233

62


3262 2923 1677 1575 1491 1441 1333 1160

1090 cm-1





20924 16980 14391 14234 13684 13672 13423 12966 12951 12910 12845 12716 12285

5874 3429 2835 2155 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3265 2924 1698 1677 1574 1442 1332 1188 1160 1089 1043 1H





17021 14375 14261 13839 13688 13528 12976 12966 12940 12729 12689 12128 5922




3262 3022 2871 1698 1677 1575 1488 1441 1404 1333 1160




C NMR (100 MHz CDCl3) 20914 16969

14398 14229 13723 13680 13211 12970 12955 12875 12719 12244 12187 5884 3429




63


3261 2927 1698 1677 1620 1575 1442 1327 1161





20907 16952 14403 14224 14204 13675 13041 (q J=324 Hz) 12965 12753 12715 12586




3259 2927 1700 1677 1574 1439 1334 1160

1089 cm-1





20924 16969 14406 14214 14018 13673 13486 13029 12973 12954 12852 12719 12515

12210 5887 3431 2835 2157 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]

+ base peak) HRMS



3235 2921 1690 1627 1571 1443 1320 1157 1092




C NMR (100 MHz CDCl3) 20943 17053

14368 14268 13730 13602 13575 13119 12955 12893 12835 12708 12642 12166 5563

3440 2841 2151 1875 MS (FAB) mz 404 ([M+Na]+) 382 ([M+H]


64

















65









oC
















66






6








) and α-d-27 (0169 h-1

) were

obtained











) were obtained

67

68

引用文献


2 For reviews see










136 15775ndash15780








13294ndash13297






1996 227ndash228





41 1737ndash1740




Chem 2007 72 5399ndash5402


69




1733ndash1736





Lett 2007 9 101ndash104








2000 2 3883ndash3885





Chem Soc 1984 106 3880ndash3882





2007 72 3326ndash3331




483ndash493








70


Chem 2015 13 8465ndash8469





3666ndash3667







2013 135 8063ndash8070




3576ndash3579















5206ndash5215



ndash5154



71






7187ndash7188



72

73

謝辞





































14














15

16

















17












18

















19









20



















21







22

23























24


























25










26









27














28












29





成に優先した





30



















31









はσC-N+











32


33

第五章結論







合成























34

















35

実験の部

36

37
















38


21 Chapter 2

Synthesis of 4














yellow oil




099H) 146 (s 801H) 123 (t 73 Hz 267H) 116 (t 73 Hz 033H) 13


16847 16833 16697 16579 16451 15895 15860 13758 13719 13415 13398 13273 13256

12927 12903 12847 12820 (2 peaks) 12802 12765 12751 12744 12737 11388 11343 8136

7304 6827 6689 6168 6116 6021 5918 5510 5156 2780 1395 1376 MS (FAB) mz 498

(M+H)+ 520 (M+Na)


+ found

4982491


39










136ndash131 (6H m)










colorless oil []D18




Hz 1H) 216 (s 1H) 125 (t 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17308 15864 13786 13173

12947 12827 12756 12750 11368 7310 7106 6080 6031 5518 5133 1422 IR (neat) cmndash1

2934 2906 2864 1736 1611 1513 1458 1368 1300 1248 1185 1102 1034 MS (FAB) mz 344

(M+H) +

366 (M+Na) +


3441862 found

3441860

40




Hz 3H) 102 (s 9H) 13

C-NMR (100 MHz CDCl3) 17339 15859 13555 13552 13308 13189

12998 12933 12764 11368 6517 6193 6071 5520 5115 2666 1919 1425 IR (neat) cmndash1

MS

(FAB) mz 492 (M+H) +


4922570 found

4922570


= -52 (c 1087 CHCl3) 1H-NMR (400 MHz






Hz 51100 H) 13

C-NMR (100 MHz CDCl3) 1684 1649 1644 1628 1591 1377 1358 1334 1292

1285 1284 1283 1282 1278 1276 1275 1140 1135 732 685 621 618 613 586 552 519 140


2983 2937 1741 1655 1514 1449 1370 1251 1207 1069 1029 MS (FAB) mz

542 (M+H) +

564 (M+Na) +


5422390 found

5422394


= -40 (c 0750 CHCl3) 1H-NMR (400



(9H m) 13

C-NMR (100 MHzCDCl3) 16830 16486 16440 16275 15921 13586 13336 12934

12846 12805 11404 11357 9957 6602 6214 6186 6140 5843 5551 5533 5527 5184 1400


2983 2938 2841 1742 1655 1514 1463 1372 1253 1211 1113 1068

1039 IR (neat) cm-1

2983 2938 1742 1655 1514 1463 1372 1253 1211 1113 1068 1039 MS (FAB)

mz 496 (M+H) +


+ 4962183

found 4962182

41


= -47 (c 0597 CHCl3) 1H-NMR (400




(t J = 75 Hz 06H) 13

C-NMR (100 MHz CDCl3) 16849 16478 16449 16280 15911 13590

13559 13550 13296 13271 13264 12984 12979 12921 12831 12773 12770 11409 11385

11356 6255 6211 6176 6128 6007 5526 5159 2676 1907 1394 1388 IR (neat) cmndash1

2958

2933 2857 1739 1656 1514 1466 1426 1370 1252 1205 1178 1111 1069 1030 MS (FAB) mz 690

(M+H)+712 (M+Na)


+ 6903098 found

6903095
















64 Hz 1H) 284 (m 2H) 131ndash128 (m 12H) 13

C-NMR (100 MHz CDCl3) 17365 15879 13165

42

12958 11381 6101 6037 5531 5135 4233 3158 3094 1442 IR (neat) cmndash1

2962 2902 2836

1734 1612 1513 1462 1367 1300 1247 1178 1034 MS (FAB) mz 326 (M+H) +

348 (M+Na)+ 121 (base


3261790 found 3261786















20100 H) 136ndash108 (m 18 H) 13

C-NMR (100 MHz CDCl3) 16896 16881 16567 16548 16430 16426

16277 15941 15888 13613 13568 13426 13367 12964 12925 12879 12717 11399 11359 6215

6195 6186 6148 5987 5527 5266 4299 4285 3076 3065 2798 2764 1399 1391 1380 IR (neat)

cmndash1

2966 2904 2839 1734 1653 1514 1462 1369 1303 1253 1212 1069 1031 MS (FAB) mz 524

(M+H) +

546 (M+Na) +


5242318 found

5242313









λ = 254 nm t=169 min t=232 min []D18


43




C-NMR

(100 MHz CDCl3) 16952 16947 16715 15882 13745 12993 12881 12829 12764 12741

11359 8131 7316 710 6719 6169 5522 5165 4505 3129 2793 1412 IR (neat) cmndash1

2979

2932 2867 1764 1735 1612 1514 1455 1392 1368 1247 1154 1032 MS (FAB) mz 498 (M+H) +

520

(M+Na) +


4982492 found 4982491


t=165 min t=191 min []D18




1H) 271 (d J 78 Hz 2H) 139 (s 3H) 119 (t J 74 Hz 3H) 13


16988 16774 15891 13718 13003 12837 12824 12778 12760 11363 8129 7337 6797 6447

6162 5523 5354 4480 3090 2788 1298 IR (neat) cmndash1

2979 2931 2869 1765 1732 1612 1514

1456 1391 1367 1248 1154 1097 1063 1031 MS (FAB) mz 498 (M+H) +

520 (M+Na) +

121 (base


4982492 found 4982491







2983 2913 2845 1767 1735 1611 1588 1514 1453 1388 1247 1177 1105

1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +


(M+H) +

4362335 found 4362335





2H) 143 (s 9H) 120 (t J 73 Hz 3H) 110 (t J 69 Hz 3H) 13


17003 16786 15895 13006 12829 11360 8126 6803 6678 6443 6156 5528 5350 4478

3092 2795 1489 1400 IR (neat) cmndash1

2976 2931 2873 1762 1734 1613 1514 1461 1390 1369

1292 1244 1152 1113 1064 1032 MS (FAB) mz 436 (M+H) +

458 (M+Na) +



4362335 found 4362335

44















086 (t J = 69 Hz 3H) 081 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1696 1672 1668

1649 1594 1381 1303 1294 1285 1283 1278 1277 1139 733 711 667 623 619 616 548

547 501 453 1394 138 2 1382 IR (neat) cmndash1

2983 2935 2869 1766 1739 1612 1514 1456

1392 1369 1301 1249 1176 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +



5422390 found 5422400






J = 73 Hz 3H) 078 (t J = 73 Hz 3H) 070 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1699 1677

1671 1657 1595 1376 1305 1286 1286 1283 12804 12800 1140 7344 6705 6415 6214 6178

6152 5673 5471 4943 4461 1397 1380 1370 IR (neat) cmndash1

2983 2935 2871 1769 1735 1612 1514

1458 1391 1369 1301 1249 1178 1098 1031 MS (FAB) mz 542 (M+H) +

564 (M+Na) +

121 (base peak)


5422390 found 5422393

45



= -16 (c 0719 CHCl3 96 ee) 1H-NMR (400 MHz




C-NMR (100

MHz CDCl3) 1692 1667 1666 1656 1589 1358 1357 1324 1300 1299 1278 1277 1137

668 633 621 620 617 552 529 492 449 268 192 1394 1380 137 IR (neat) cmndash1

2961

2934 2859 2369 2315 1769 1736 1650 1613 1514 1468 1428 1390 1370 1301 1251 1177 1108

1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


C38H48NO9Si (M+H) +

6903098 found 6903098







(s 9H) 099 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1695 1676 1670 1660 1589 1362

1357 1323 1318 1303 1300 1280 1278 1267 1136 639 6206 6202 614 597 552 483

441 269 190 1396 1392 136 IR (neat) cmndash1

2961 2934 2859 2369 2315 1769 1736 1650 1613

1514 1468 1428 1390 1370 1301 1251 1177 1108 1035 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


6903098 found 6903098


46












124 (t J = 68 Hz 3H) 114 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 1697 1671 1666

1591 1304 1274 1137 655 622 6203 6196 555 553 493 453 427 320 307 139 138 IR

(neat) cmndash1

2966 2937 2868 1770 1734 1613 1514 1464 1389 1368 1301 1248 1178 1095 1033

MS (FAB) mz 524 (M+H) +

546 (M+Na) +


(M+H) +

5242318 found 5242318



= 24 (c 0551 CHCl3 91 ee) 1H-NMR (400 MHz




C-NMR (100 MHz

CDCl3) 1699 1672 1666 1654 1591 1303 1276 1137 643 6219 6219 6212 6198 560

553 485 453 428 303 291 140 138 IR (neat) cmndash1

2969 1769 1738 1613 1514 1464 1389

1369 1301 1248 1178 1034 MS (FAB) mz 690 (M+H) +

712 (M+Na) +


mz 524 (M+H) +

546 (M+Na) +


5242318 found 5242313












47




















13659 13031 12849 12833 12805 12760 12157 12144 11379 8783 8749 7347 6855 6695 5522










b = 120516(8) Aring = 90deg

c = 271658(19) Aring = 90deg


48

Z 4



F(000) 1608















49

22 Chepter 3














122 (t J = 69 Hz 3H) 13

C-NMR (100 MHz CDCl3) 17340 15856 13834 13206 12945 12821

12758 12747 11357 7557 7075 6468 6064 5518 5170 1635 1421 IR (neat) cmndash1

2979 2932

2838 1734 1612 1512 1459 1373 1299 1247 1184 1159 1094 1032 MS (FAB) mz 358 (M+H) +

380 (M+Na) +


3582018 found

3582010














(m 356H) 133ndash118 (m 1115H) 111 (t J = 76 Hz 084 H) 13


50

16816 16636 16551 16455 16405 16302 16273 15888 15856 13824 13766 13612 13528

13398 13306 13096 12955 12945 12878 12832 12827 12809 12767 12757 12751 12726

12660 11377 11329 7416 7161 7135 7080 6563 6221 6195 6167 6118 5517 7167 1732

1663 1393 1385 1370 IR (neat) cmndash1

2981 2936 2905 1738 1652 1513 1457 1372 1250 1205

1177 1096 1067 1030 MS (FAB) mz 556 (M+H)+ 578 (M+Na)



5562547 found 5562547























51







13C-NMR (100 MHz CDCl3) 17382 15864 13832 13180 12947 12821 12747 11365 7634

7091 6465 6065 5522 5147 1657 1431 IR (neat) cmndash1

2979 2933 2837 1730 1611 1513 1460

1372 1302 1247 1185 1108 1033 MS (FAB) mz 358 (M+H) +

380 (M+Na) +



3582018 found 3582023









a colorless oil



oC) 737ndash720 (m


131ndash115 (m 12H) 13

C-NMR (100 MHz CDCl3) 16879 16872 16586 16491 16444 16396

16272 15920 15885 13827 13754 13584 13551 13513 13355 12972 12894 12852 12837

12824 12798 12787 12778 12749 11403 11355 7490 7341 7219 7117 6505 6219 6214

6185 6151 6112 5525 5520 5151 1641 1619 1397 1386 IR (neat) cmndash1

2982 2937 2905

1739 1656 1613 1513 1450 1373 1252 1203 1095 1070 1030 MS (FAB) mz 556 (M+H) +

578


+ found 5562549





52








094 (t J = 74 Hz 3H) 085 (t J = 74 Hz 3H) 13

C-NMR (100 MHz C6D6) 1702 1677 1673 1663

1598 1395 1308 1303 1290 1289 1281 1279 1145 784 716 713 628 625 621 5529

5526 513 465 161 1454 1450 1445 IR (neat) cmndash1

2981 2925 1766 1739 1648 1612 1514

1461 1390 1371 1301 1249 1178 1096 1031 MS (FAB) mz 556 (M+H) +



5562547 found 5562545







C-NMR (100

MHz C6D6) 1707 1671 1667 1651 1593 1387 1312 1300 1285 1283 1277 1276 1138 766

719 716 624 619 616 546 542 505 466 140 139 124 IR (neat) cmndash1

2983 2938 1766 1739

1613 1514 1459 1373 1248 1177 1148 1097 1032 MS (FAB) mz 556 (M+H) +

121 (base peak)


5562547 found 5562549




C-NMR (100

MHz CDCl3) 17035 16717 16663 16632 15871 13750 12961 12854 12832 12772 12766

11357 7216 7007 6893 6202 6187 5606 5520 4872 4588 1547 1403 1399 1396 IR (neat)

cmndash1

2983 2914 2845 1767 1735 1611 1588 1514 1453 1388 1248 1177 1105 1032 MS (FAB)

mz 556 (M+H) +


5562547 found

5562546



53





















54











3033 2359 2306

1737 1677 1610 1585 1537 1516 1486 1394 1322 1248 1179 1117 1061 1033 1006 MS (FAB) mz

1095 (M+Na) +


10949589 found

10949577







Space group C2221


b = 30665(2) Aring = 90deg

c = 134874(12) Aring = 90deg


Z 8



F(000) 4544











55











Space group C2(5)


b = 75202(3) Aring = 1025865(14)deg

c = 236650(9) Aring = 90deg


Z 8



F(000) 2368















56

23 Chapter 4















3560 3092 3010 2924 1706 1673 1627 1573 1440 1410 1346 1290












57






1H




3298 3058 2958 1678 1629 1581 1448 1419 1358




194ndash187 (1H m) 13

C NMR (100 MHz CDCl3) 20910 16553 14294 13841 13754 13634

12973 12914 12858 12767 12711 12640 12437 5337 3368 2522 2142 MS (ESI) mz 390


+ 3901134 found 3901138










3265 3028 2924 1676 1573 1494 1449 1330 1190 1159 1088 1H



245ndash228 (5H m) 13

C NMR (100 MHz CDCl3) 20938 17011 14378 14253 13821 13688 12966

12943 12908 12843 12727 12699 12155 5944 3429 2837 2156 MS (ESI) mz 390 ([M+Na]+)

58






29




30 respectively


3276 1684 1631 1599 1518 1432 1348 1162 1089




(2H m) 205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20885 16645 14728 14557 14346

13728 13533 12935 12922 12736 12703 12552 12378 5275 3364 2545 2144 MS (FAB) mz

435 ([M+Na]+) 413 ([M+H]


+

4350991 found 4350991


3276 2928 1683 1631 1584 1511 1432 1335 1307 1249 1165 1092



59


(1H m) 13

C NMR (100 MHz CDCl3) 20919 16528 15904 14286 13759 13653 13058 12975

12912 12769 12714 12422 11392 5523 5299 3372 2519 2141 MS (FAB) mz 420 ([M+Na]+)



3269 2922 1684 1630 1583 1491 1426 1338 1162 1091 1H NMR





16579 14313 13747 13695 13600 13362 12952 12922 12872 12785 12709 12477 5285

3370 2529 2144 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3272 2921 1684 1630 1428 1338 1162 1092 1H NMR (400 MHz




(1H m) 13

C NMR (100 MHz CDCl3) 20913 16534 14287 13759 13747 13651 13548 12978

12926 12912 12714 12633 12421 5321 3370 2520 2142 2098 MS (ESI) mz 404 ([M+Na]+



3273 2922 1685 1630 1585 1488 1426 1338 1071 1011 1H NMR



60


m) 13

C NMR (100 MHz CDCl3) 20906 16581 14315 13748 13745 13593 13166 12951

12923 12818 12708 12481 12176 5292 3370 2529 2145 MS (FAB) mz 470 ([M+2+Na]+ base


[M+Na]+ 4680245 found 4682045


3271 2923 1687 1630 1585 1425 1328 1163 1121 1068 1018 1H




205ndash196 (1H m) 13

C NMR (100 MHz CDCl3) 20904 16607 14322 14234 13740 13574

12986 (q J=324 Hz) 12939 12924 12703 12683 12552 (q J=27 Hz) 12506 12385 (q J=2708

Hz) 5310 3368 2535 2137 MS (FAB) mz 458 ([M+Na]+) 436 ([M+H]




3267 1685 1631 1594 1434 1339 1162 1092 1H NMR (400 MHz




C NMR (100 MHz CDCl3) 20900 16598

14315 14039 13741 13579 13450 12985 12948 12923 12788 12705 12660 12489 12462

5290 3368 2532 2143 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3261 1692 1630 1581 1491 1427 1342 1321 1162

61




m) 13

C NMR (100 MHz CDCl3) 20965 16573 14293 13732 13644 13635 13629 13093

13990 12901 12811 12740 12734 12617 12420 5106 3372 2528 2144 1981 MS (FAB) mz

404 ([M+Na]+) 382 ([M+H]


+)

4041296 found 4041296


3265 2925 1698 1677 1575 1522 1442 1346



m) 244 (3H s) 241ndash237 (2H m) 13

C NMR (100 MHz CDCl3) 20879 16906 14755 14539

14435 14204 13663 12977 12970 12805 12716 12403 12280 5878 3433 2834 2156 MS


+ 4350985

found 4350980


3263 2925 1702 1676 1611 1574 1512 1442 1329 1253 1159 1088




C NMR (100 MHz CDCl3) 20939 17019

15960 14381 14266 13687 13026 12972 12942 12828 12731 12116 11446 5895 5527


[M+Na]+ 4201240 found 4201233

62


3262 2923 1677 1575 1491 1441 1333 1160

1090 cm-1





20924 16980 14391 14234 13684 13672 13423 12966 12951 12910 12845 12716 12285

5874 3429 2835 2155 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]




3265 2924 1698 1677 1574 1442 1332 1188 1160 1089 1043 1H





17021 14375 14261 13839 13688 13528 12976 12966 12940 12729 12689 12128 5922




3262 3022 2871 1698 1677 1575 1488 1441 1404 1333 1160




C NMR (100 MHz CDCl3) 20914 16969

14398 14229 13723 13680 13211 12970 12955 12875 12719 12244 12187 5884 3429




63


3261 2927 1698 1677 1620 1575 1442 1327 1161





20907 16952 14403 14224 14204 13675 13041 (q J=324 Hz) 12965 12753 12715 12586




3259 2927 1700 1677 1574 1439 1334 1160

1089 cm-1





20924 16969 14406 14214 14018 13673 13486 13029 12973 12954 12852 12719 12515

12210 5887 3431 2835 2157 MS (ESI) mz 426 ([M+2+Na]+) 424 ([M+Na]

+ base peak) HRMS



3235 2921 1690 1627 1571 1443 1320 1157 1092




C NMR (100 MHz CDCl3) 20943 17053

14368 14268 13730 13602 13575 13119 12955 12893 12835 12708 12642 12166 5563

3440 2841 2151 1875 MS (FAB) mz 404 ([M+Na]+) 382 ([M+H]


64

















65









oC
















66






6








) and α-d-27 (0169 h-1

) were

obtained











) were obtained

67

68

引用文献


2 For reviews see










136 15775ndash15780








13294ndash13297






1996 227ndash228





41 1737ndash1740




Chem 2007 72 5399ndash5402


69




1733ndash1736





Lett 2007 9 101ndash104








2000 2 3883ndash3885





Chem Soc 1984 106 3880ndash3882





2007 72 3326ndash3331




483ndash493








70


Chem 2015 13 8465ndash8469





3666ndash3667







2013 135 8063ndash8070




3576ndash3579















5206ndash5215



ndash5154



71






7187ndash7188



72

73

謝辞





































title 不飽和カルボニル化合物への共役付加を基盤とする選択 ......1...

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