YIides and Related Compounds

BY B. J. WALKER

1 Introduction During the past few years it has become increasingly obvious that the different phosphorus-based olefin syntheses are largely complementary. These reactions now offer excellent methods for highly stereospecific synthesis of most olefins, with the exception of some conjugated E alkenes and very highly substituted alkenes.

2 Methylenephosphoranes Recent advances in the chemistry of ylides in general' and of P-heterosubstituted phosphorus ylides2 in particular have been reviewed.

2.1 Preparation and Structure. - The electronic structure of the simplest ylide ( H 3 6 - E H 2 ) has been calculated using ab initio molecular orbital theory at the GVB+POL-CI level .3 Both n.m.r. spectroscopic data and X-ray analysis show that the carbanionic centre in cyc lobu ty l idene t r ipheny lphosphorane is not quite planar and that the ylide P-C bond has a considerable degree of double- bond character. 4

Continuing their investigation of carbodiphosphoranes, Schmidbaur's group has reported attempts to prepare those based on the 1 , 3-diphosphanindane skeleton. The semi-ylides ( 2 1 are formed by base-treatment of the cyclic bisphosphonium salt (11, but are readily hydrolysed to (3). Diylides of the type ( 4 ) , but not carbodiphosphoranes, can be prepared from (2) by transylidation. Carbodiphosphoranes of types ( 5 ) and ( 6 ) can be prepared from their semi-ylide salts by treatment with butyl-lithium. The cyclic bis(ylide)-bis(salt) ( 8 ) is formed by spontaneous dimerization of solutions of the vinylphosphonium salt ( 7 ) through Michaeladdition of phosphine to the activated alkene.6 been confirmed by X-ray analysis. A series of P-amino-substituted carbodiphosphoranes ( 9 ) have been prepared and shown to have fairly predictable properties. However, an &-ray study of hexakis- (dimethy1amino)carbodiphosphorane ( 9 , R =R =R =NMe 1 indicates a previously unobserved linear arrangement at ylidic carbon. '

The structure of ( 8 ) has

1 2 3 2

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8: Ylides and Related Compounds 283

# \R2

( 5 ) R’ = Ph, R2 =Me

(6 ) R 1 = R 2 = Ph

2 ;;H2 1- - +,c\

Ph2P PPh, Me

P h ,PMe

1 2 3 R ,P=C = P(NMe, )R R

( 9 )

Ph’ ‘Me

(4)

2 121 1-

Surprisingly, the lithiated phosphine (10) undergoes reaction with electrophiles at phosphorus, rather than carbon, and thus provides a route to a variety of P-substituted phosphonium ylides including

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284 Organophosphorus Chemistry

1 R' R H a l Ph2P- CEiMe,), - Ph2P=C(SiMe3I2

(10) ( 1 1 )

Li

'12 XHal, I X

Ph,P' 'PPh,

(Me3Si ),C C(SiMe,), II It

Ph,P-PPh , I I I

(Me,Si ),C CH(SiMe,),

(13)

(15)

PPh, I I

2+

2 B r -

(16) n = 3 , 4

the unknown !-,acylphosphoranes (11, R1=R2CO) . A variety of di- ylides ( 1 2 ) have been synthesized by an analogous method and in one case shown to be in the alternative prototropic form ( 1 3 ) in the solid state. In an investigation of tris(phosphoniurn1 methanide salts and ylides, Schmidbaur has shown by 31P n.m.r. spectroscopy that the salt (151, formed by phosphinylation of hexaphenylcarbodiphosphorane ( 1 4 ) , has non-equivalent triphenyl- phosphorus groups due to restricted rotation of the diphenyl- phosphinyl group .9

salts (16). Other examples synthesized include the cyclic

Vinylphosphonium salts have been used extensively in the generation of ylides. The potentially useful synthetic inter- mediates (17) have been synthesized by the reaction of phosphonium ylides with tetrarnethylformamidinium chloride . lo Acid hydrolysis,

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8: Ylides and Related Compounds 285

CI -

/ ( l l ) Hydrolysis

R 0-

NMe2 /

Ph3P +7==lH (1 9)

0

Ph3P +X H

Me (20)

+

KSR Reagents: i, NaH, THF; i i , Ph3P

Scheme 1

followed by treatment with base, converts ( 1 7 ) into the formyl ylides (181, and (17, R = H ) is deprotonated with sodium amide to give the allenylidene ylide ( 1 9 ) . The reaction of l-mercaptovinyl- phosphonium salts with the anions of ketones has been used to prepare a variety, e.g. (201 , of highly functionalized cyclo- pentenes via intramolecular Wittig reactions (Scheme 1) .I1 analogous phosphonium salt ( 2 1 ) has been generated in situ and shown to react with various enolates to give ylides, e.g. ( 2 2 ) . 1 2 Depending on the conditions used, these ylides react to give a variety of synthetically useful products; however, attempts to use the reaction to generate the fused BC ring fragment ( 2 3 ) of bruceantin gave only low yields . I 3 1-Phosphorylenamines ( 2 5 ) , prepared from the phosphonate ( 2 4 1 , give on base-treatment the delocalized anions ( 2 6 ) . I 4 In almost all cases ( 2 6 ) react regio-

-- The

-

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286 Organophosphorus Chemistry

-bcmMI *PPh3 COOMe

SPh ( 2 1 ) ( 2 2 )

COOMe

Me0

R ' ! R4

i , v i - lv 1.

R RY-:: 3

R RYooH 4

3 4 Reagents: i , 6u"Li; ii, ( M e S I 2 ; i i i , A ; iv , A X ; v , H 2 0 ; v i , R X

Scheme 2

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8: Ylides and Related Compounds 287

specifically and stereospecifically in the u-position with electro- philes. Hydrolysis of the alkylated products provides a route to a large variety of multiply-substituted carboxylic acids (Scheme 2 ) .

+- Ph36CFzBr €3; + R,P - [Ph3PCF2] + R3PBr

Ph,P + [CFz]

+ R3PBr2 R,P + R,PCF,Br Br- - ~ R3P=CF,

Difluoromethyl ylides (27) are thought to be formed and to dissociate to give difluorocarbene in the exchange of the bromo- difluoromethyl group which takes place when (bromodifluoromethyll- triphenylphosphonium bromide is treated with tertiary phosphines or phosphites . I5 of sodium hydroxide, mixtures of chloroform, triphenylphosphine, and benzaldehyde give l,l-dichloro-2-phenyl ethene. l6 suggestion that the reaction involves the formation of dichloro- carbene, and hence dichloromethylene ylide in situ, is supported by similar reactions of other halides which are known to give carbenes under these conditions. The method was used to prepare a variety of vinylcyclopropane derivates, e.g. -- ( 2 8 ) , related to pyrethrins, although in some cases direct olefination with the appropriate phosphonate anion was shown to be superior. The reaction of dibromomethylenetr iphenylphosphorane with 2-halopent- 2-enals leads to the formation of the expected diene ( 2 9 ) and in some cases, depending on the conditions, 1,1,4-tribromohex-l-en-3- one (30) . I7 (30).

ketones from straight-chain dialdehydes .I8

Under phase-transfer conditions in the presence

The

A mechanism has been proposed for the formation of

Bestmann has reported a new route to unsaturated macrocyclic Stereospecif ic 7-

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288 Organophosphorus Chemistry

1 R SCIC-CH

A'SCHC12 + Ph,P +

a C H O Ph3P, CBg *

X = F, CI, Br

NaOH T E B A

Ph,P=CH(CH,), COO- Na'

( 3 4 )

olefination of ( 3 1 ) with the appropriate carboxylate ylide ( 3 2 ) followed by reaction with the cumiilene ylide ( 3 3 ) offers a new method of generating B-keto ylides ( 3 4 ) . Deprotection and intra- molecular Wittig reaction gives (E,Z)-cyclodienones ( 3 5 ) . The insoluble polv(styrene)-bound phosphonium salts ( 3 6 ) and ( 3 7 ) have been prepared and, throiigh conversion to the corresponding ylides and reaction with aldehydes, used to prepare isomeric mixtures of

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8: Ylides and Related Compounds 289

w l : H 2 C ~ M e l - - CH COOEt

Ph

Br- (36)

@ = polymer support

@53 Ph I Me

Br- (37)

Reagents: i , NaOEt, EtOH; i i ,

Me Me CH=CH C = CHCH= CHC = CHCOOEt

Me

i , iii /

MwcHo Me

... I l l , EtOOC a COOEt

Scheme 3

ethyl retinoate (Scheme 3 ) .19 idene)phosphorane (38) offers a method of introducing the 3 , 4 - unsaturated aldehyde function v i a the Wittig reaction.

Triphenyl(4-trimethylsiloxybutyl-

20

Ph,P=CH (CH2),0Si Me,

(38)

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290 Organophosphorus Chemistry

The reaction of arylhyrlrazonyl chlorides ( 3 9 ) with triethyl- amine and triethylphosphine gives arylazomethylenetriphenyl- phosphoranes (41) via reaction of the intermediate nitrile imine (40) with phosphine.2’

22 disulphide to give 4-aryl-1,3,4-thiadiazoline-5-thiones (42). The first examples of d i a l k y l b o r o n - s u b s t i t u t e d phosphonium

The phosp oranes (41) react with carbon

ylides (43) have been prepared by reaction of dialkylchloroboranes with alkylidene-ylides. 2 3 The compounds are crystalline, but rather

CI PPh, ArNHN==C ’ - A r f i N = k O O E t - ArN=NC/’

(39) (40) (41 1 \COOE t ‘ COOEt

CCOOtt s 4 c \ s /

1 2 1 2 + 1 2 Ph3P=CHR + RZBCI Ph,P=CR B R Z + Ph,PCH,R CI -

(43)

Ph

(44 1

unstable thermally. Transition-metal complexes, e.g. (44), of a number of reactive phosphorus 24y25 and arsenicz4 Z d e s have been prepared by reaction of the appropriate ditertiary phosphine or arsine with sulphur ylide complexes.

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8: Ylides and Related Compounds 29 1

2.2 Reactions of Methylenephosphoranes 2.2.1 Aldehydes.- A further study of the Wittig reaction using 31P

n.m.r. spectroscopy to observe directly the oxaphosphetane inter- mediates has both confirmed results obtained by other methods and produced some new information. *' triphenylphosphorane, generated as shown, with benzaldehyde gave - cis-(45; in a 3 . 8 : l ratio (Scheme 4). This ratio fell to approximately 1:l as the reaction proceeded and the cis:trans ratio of alkene products (1.5:l) did not reflect the original proportions of the oxaphosphetanes (45) and (46). From these results and a study of a similar reaction with hexanal it is concluded that: (a) cis oxaphosphetanes decompose to alkene faster than trans; ( b ) the

The reaction of n-butylidene-

6p -61.4 ppm) and trans-(46; 6p -63.8 ppm) oxaphosphetanes

R

Ph3P=CHPr"

+ RCHO

+ Ph3P- 0 Ph3P(CH2I3Me Br-

(45) ( 4 6 )

+ H Ph, P

i s v

+ Pr" Ph, P

HO*-H R

HO/f-'H R

Reagents: i, LiHMDS; i i , RCHO; i i i , HBr, iv, Base

Scheme 4

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292 Organophosphorus Chemistry

oxaphosphetmes derived frombenzaldehyde, but not those derived from hexanal, undergo equilibration at a rate competitive with the rate of decomposition (possibly y& hetaine reversibility); (c) the smaller alkene z/E_ ratios observed for reactions with aromatic aldehydes, compared to those with aliphatic aldehydes, are caused by oxaphosphetane interconversion in the former case rather than differences in the ylide-aldehyde condensation step. These results are supported by isolation snd ba.se-indiiced decomposition of the erythro (47) and threo (48) 6-hydroxyphosphoniurn salts corresponding to ( 4 5 ) and (46). Some similar experiments were also carried out with e t h y l i d e n e t r i p h e n y l p h o s p h o r a n e since this has been used by both Vede js and Schlosser in their studies; however, the 31P resonances of the isomeric oxaphosphetanes were not well resolved in these cases. Unlike similar reactions of reactive ylides, highly stereoselective olefination of aldehydes using moderately stable ylides (e.g. benzylidene- or allylidene-) has not been possible. Vedejs has now shown that dienes can be synthesized with

-

R’ ‘A CR2 R3 + 1 2 3 4

Ph,(ALkyl)P=CHC=CR R + R CHO - R

(49)

R’ ‘A CR2 R3 + 1 2 3 4

Ph,(ALkyl)P=CHC=CR R + R CHO - R

(49)

a high degree of E selectivity from salt-free allylic ylides (49) by replacing one of the phenyl groups attached to phosphorus by an alkyl group.27 selectivity in the Wittig reaction by steric interactions with phenyl substituents on phosphorus, these results clearly have implications for the detailed mechanism of that reaction. Vedejs argues briefly but convincingly that a key element of Bestmann’s proposals28 are unlikely. olefination of changing the phosphorus group has been further in~estigated.~~ reactions using five- or six-membered cyclic phosphonates than from those using phosphinates or phosphine oxides. The rates of Wittig reactions of stabilized ylides with aldehydes increase markedly and the proportion of trans alkene increases marginally at very

In view of Schlosser’s attempts28 to explain cis

The effect on the stereochemistry of

Higher yields of z alkenes were obtained from

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8: Ylides and Related Compounds 293

high pressures.30 effects, even of apparently remote groups, can play in olefination is given by the synthesis of (53) .31 the aldehydic ketone (50) gives (53) in good yield, while a similar

A demonstration of the important role that steric

A Wittig reaction of ( 5 2 ) with

FHO

Me

+ P h3P= CCOOMe I CH - COOMe

( 5 0 ) R, = 0

Me v

P h3P= CCOOMe I CH , COOMe

COOMe

COOMe

Me

+ Ph,PMe

R3Ti , ' P P h 2 . E p (ii) Me1 [.-dwl ( 5 4 )

reaction of the corresponding ketal ( 5 1 ) gives only traces of the ketal of (53).

32 New routes to z or E 1,3-dienes have been reported. Reaction of the (dipheny1phosphino)allyltitanium reagent (54) with aldehydes followed by methylation and base-treatment gives moderate to good yields of almost pure z 1,3-dienes. The alternative g dienes are available from reactions of aldehydes with the carbanion of allyldiphenylphosphine oxide. The ylide (561, derived from the iron carbonyl-diene complex (55), undergoes a Wittig reaction with the aldehyde (57) to give two isomeric iron pentaene complexes ( 58 1 . 3 3 carbanion gives exclusively the all-trans isomer of (58).

A similar reaction using the analogous phosphonate

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294 Organophosphorus Chemistry

(55) (56)

Ethanediylidene-2,2'-his(l,3-dithioles) ( 5 9 ) , a new type of electron donor, have been prepared by Wittig reactions of ( 1 , 3 - dithio1idene)phosphoranes with 2-formylmethylene-l,3-dithioles. 34

X-

d Ris S

A variety of polyenes of the type ( 6 2 ) have been prepared using a variety of phosphorus-based olef in syntheses. 3 5 generally successful method involved Wittig reaction of the ylide

However, the most

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8: Ylides and Related Compounds 295

( 6 0 ) with an appropriate aldehyde ( 6 1 ) .

SePh

(63) (64)

A variety of allylic selenides ( 6 3 ) 3 6 and 1-substituted 3- phenylseleno-1 , 3-butadienes ( 6 4 ) 37 have been prepared by Wittig and phosphonate olefination of the corresponding a-phenylseleno- aldehydes and a-phenylselenoenals, respectively. What appears to be a general method for the preparation of secondary allylamines (essentially from any primary amine) is available from Wittig reaction of the ylide anion ( 6 5 ) . 38 E selectivity was observed in those alkenes formed from aromatic, viny1,or highly sterically hindered aldehydes; results which are analogous to those obtained from Wittig reactions with ylides containing electron-donating groups (e.g. - 0 - , C 0 2 - ) in the side-

Interestingly substantial

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296 Organophosphorus Chemistry

Li H P h,P -"R' + R 2 CHO - R e C H R *

Ph3P= CH(CH,), NR,

chain. The use of aminoa lky l idene t r ipheny lphosphoranes of type (66) in the Wittig reaction has a l s o been investigated. 39

a-Cyclopropylidene acetals (67) and hence the corresponding aldehydes, are available from the reaction of a-keto- or a-formyl

I R3

(67)

Ph3P=CHR + (EtO) ,CHCHO - RCH=CHCH(OEt

( 6 8 )

OCOMe

X = H, OCOMe, O(THP), O(Alkyl1, OSiRj "YlOMe X

acetals with cvclopropylidenetriphenylphosphorane.40 Bestmann has reported another synthesis of largely z a,~-unsaturated acetals and aldehydes by Wittig-olefination of glyoxal semiacetal (68). It is also worth noting that mixed acetals of the type (691, which are often more stable than the parent aldehydes, undergo both Wittig- and phosphonate-o lef ina t ion .

41

42

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8: Yiides and Related Compounds 297

The highly reactive arylcarbonyloxyalkyl idenephosphoranes ( 7 0 )

have been prepared at -60' from the corresponding phosphonium salts.43 These compounds will undergo the Wittig reaction at

R' COOCHR 2 + PPh, CI- * [R'COOSR2&Ph3]

A r CH 2CORL [x' R PPh, j 2

R'COCOR + Ph3P

Reagents: i , LiNPr' ; i i , ArCHO; i i i , KOH, MeOH; iv, R.T. 2

S c h e m e 5

- 5 0 ~ ~ ~ 9 ~ ~ (thus providing a new route for aldehyde to alkanone transformation) and on warming to room temperature give unsymmetrically substituted 1,2-diketones, probably via the zwitterions ( 7 1 1 (Scheme 5 ) .

It is worth noting that a Wittig reaction with acrolein gave much higher yields with a phosphorane derived from the corresponding phosphonium tosylate than that derived from the phosphonium iodide .45 The use of methylene ylide to prepare 4 ( 5)-vinylimidazole from the corresponding aldehyde leads to competing reductions of the aldehyde to alcohol unless a two-fold excess of ylide is used. Vinyl epoxides can be obtained in good yields from the corresponding aldehyde or ketone by reaction with allylic arsonium ylides ( 7 2 ) .

46

47

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298 Organophosphorus Chemistry

2.2.2 Ketones. - A new one-pot synthesis of furans,by reactions of a-bromoketones with (a-formylethy1idene)triphenylphosphorane (73) followed by treatment with n-butylmercaptide and then with mercuric sulphate, has been reported (Scheme 6) .48 hutenolide synthesis is provided by the reaction of (2,2-diethoxy- viny1idene)triphenylphosphorane (74) with enolizing 1,2-diketones,

A new

I

Ph,P=C(Me)CHO

(73 ) Me

0

+ 0 -C(Me)PPh3

\ 0

Reagents: i , . i i , BUS-; i i i , Wittig; i v , HgS04

ke

iii, iv I

6 Me

U Me

Scheme 6

followed by acid hydrolysis (Scheme 7) .49 pyrones ( 7 5 ) are also formed. A convenient route to a variety of chloro-3-cumulenes is provided by Wittig reactions of the 3-chlorocumulene ylide (77), obtained directly from the dichloro- propenylphosphonium salt ( 76) . 5o

Under certain conditions

4.9-Dihydropyrazolo[ 1,5-11] -

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8: Ylides and Related Compounds 299

P h 3 P - 1 2 3 >(OEt l2

R R CHCOCOR t Ph,P=C=C(OEt), - R’ R2C 0

Y (74)

R CO

1 , i i

R’ R’C

MeCO

M e

MeC

Reagents: i , -Ph3PO; i i , H30+

Scheme 7

CI C I

H

2(Me3SiI2NLi Ph3P=C=C=C, / *

(76) R~R’CO 1

isoquinolines [eAg.(79)] with the phosphoranes ( 78 1 . 51

have been obtained by reaction of ketenes

The Wittig reaction of adamantanone with the appropriate aminoalkylidene ylide followed by hydrogenation has been used to prepare 2- (aminoalkyl )adamantanes ( 8 0 ) . 52 reactions offer routes to 4-azahomoadamant-3-ene ( 8 1 ) and 4-aza-4- homobrend-3-enes ( 82 1 . 53

Intramolecular aza-Wittig

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300 Organophosphorus Chemistry

R' 2 3

"\ A p t , + R R C=C=O P h 3 P q N

Me

(78)

(81 1

19 Y

(82) Y = H2 or 0

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8: Ylides and Related Compounds 30 1

Tetrabromo- and tetrachloro-2-quinones, unlike less-reactive 54 quinones, react with phosphoranes ( 8 3 ) to give 1,3-dioxoles.

X

X x* x

X = CI or Br

+ Ph,P=CAr2 .-- X x*o>Ar* 0

( 8 3 ) X

2.2.3 Miscellaneous Reactions.- Phosphorus-carbon prototropic tautomerism [e.g.(84)1 has been reviewed.

a-acylphosphoranes has been extended to thioacetylenes (85). Known reactions of ( 8 5 ) provide routes to a wide variety of other acetylenes not directly available from the thermolysis reaction, which only yields acetylenes carrying electron-withdrawing groups.

55

The well-known acetylene synthesis involving thermolysis of 56

H R,P=CR, f-- R2P-CHR,

230 “C 5 x mm Hgf

R ’ C = CSR,

(85 1

ii, i i i R ’ C E C R ~ R’

Ph3P=CCOR2 - R’COCOR2

Reagents: i , (Ph0l3P, 03; i i , HZNNH2; iii, C u C I , py, O2

Scheme 8

Acetylenes can also be prepared by oxidation of suitably substituted acyl ylides with a phosphite-ozone adduct to give a-diketones, followed by conversion to dihydrazones and further oxidation (Scheme 8). 57 However, at best, overall yields are only moderate.

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302 Organophosphorus Chemistry

A new route to 2,2-substituted 1,3-indanediones ( 8 8 ) from phthalic anhydride has been developed. 58 chloride-ester ( 8 6 ) followed by reaction with ethoxycarbonyl- methylenetr iphenylphosphorane gives ( 8 8 ) via (87),which can be

Conversion to the acid

+ 2 Ph,P=CHCOOEt COOEt

COOR acocl (86 1 0

@cooEt

0

OR

-i-

6 p* 0

R

/CN

Ph R ' P O + Ph3P=C \

(89) - +

R R

(90)

isolated under certain conditions. The reactions of l-cyano- benzyl idenetr iphenylphosphorane with cyclopropenones have been studied and shown to give a variety of products including the betaines ( 8 9 ) and the indolizine diones ( 9 0 ) .59 These products

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8: Ylides and Related Compounds 303

are quite different from those obtained from similar reactions of cyclopropenones with phosphoranes possessing a-hydrogen atoms. A general synthesis of a-branched a-ketocarboxyiic acid anilides (91) i s provided by the reaction of acylmethylene ylides with phenyl isocyanate followed by hydrolysis .60 The pyran-based

NPh

phosphoranes (93) are the products [4+2]-cycloaddition of phosphacumulene ylides (92) with a,B-unsaturated ketones. 61

PPh3

X

Ph,P=C=C=X + R'COCH=CHR* - (92) X = 0, NPh, o f R'

PhCOOH I R

Benzoic acid-catalysed Hofmann degradation of ( 9 3 ) gives the highly coloured pyran derivatives (94).

by reaction of 3-methylenespiro[5.5]undeca-1,4-diene (95) with methylenetr iphenylphosphorane in DMSO gave (96) as the major product and only traces of (97 1 .62

Attempts to prepare d i s p i r o [ 2 . 2 . 5 . 2 ] t r i d e c a - 4 , 1 2 - d i e n e (97)

The formation of (96) was

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304 Organophosphorus Chemistry

(95) (96) 1 2 (97) R = R = H

(98) R ' = R2 = Me

shown to be due to competing reaction of (95) with methylsulphinyl carbanion. Increasing the nucleophilicity of the phosphonium ylide leads to a greater proportion of cyclopropane product, e.g. 2-Propyl idenetr iphenylphosphorane gives a high yield of (98). The formation of methylenephosphonium cations ( 1 0 0 ) by chloride

-

CI

(R,N12P=CR R A I C $ or 3 I 1 2

*g BF4

(99) (100)

abstraction from P-chloromethylene ylides ( 9 9 ) has been confirmed by 'H, "C, 31P,and 2 7 A l n.m.r. spectroscopy and in one case by isolation. 6 3

The synthesis and chemistry of metal complexes of phosphonium 64 ylides have been reviewed. Copper, silver,and gold complexes

(101) of hexaphenylcarbodiphosphorane have been prepared.65 iron hydride complex ( 1 0 2 ) reacts with methylenetr imethylphosphorane to give ( 1 0 3 1 , probably via proton abstraction by the highly basic yl ide and subs ti tution . 66Keto-stabi li zed ylides of both phosphorus and arsenic react with bis(l,5-~yclooctadiene)nickel to form complexes which catalyse ethylene oligomerization.

The

67

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8: Ylides and Related Compounds 305

(101) M = Cu, Ag,Au

(102) (103)

3 Reactions of Phosphonate Anions

Several PO-olefinations [e.g.(104)1 primarily concerned with the synthesis of phosphonates by ene reactions of 2-phosphonacrylates (see a l s o Chapter 3 ) . It has been reported that the dianion ( 1 0 5 ) only provides good yields of alkenes, in reactions with aldehydes and ketones, when in the form of its potassium, rather than sodium, salt.69

are described in a report 68

In the presence of

COOMe COOMe

(104)

(105)

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306 Organophosphorus Chemistry

lithium salts 8--ketophosphonates can be deprotonated by weak bases, e.g. amines, which allows olefination reactions with base-sensitive aldehydes and phosphonates. 7 0 applied to several examples where previously attempted olefination has led to competing epimerization, elimination,or low yields. Stereochemical control in phosphorus-based olefin synthesis continues to be of interest. It is reported by Russian workers that by the appropriate choice of conditions the reaction of the phosphonamide-stabi l ized carbanions ( 1 0 6 ) with aldehydes can be

- This method has been successfully

induced to give entirely erythro adducts (which appear to be the thermodynamically stable products) or a mixture of erythro and threo isomers. 71 conditions gives & alkenes stereospecifically.

Heating the erythro adducts under neutral

Phosphonate-based routes have been used to prepare a variety of polyenes. In a synthesis of polyenic enol ethers ( 1 0 7 ) , the hydroxyphosphonate intermediates can be isolated and reacted with base to give (107); alternatively the reaction mixture obtained from aldehyde and phosphonate carbanion forms (107) directly on prolonged heating. 7 2 E, stereoselective, but the yields are at best moderate. Highly conjugated A4y4'-bis(4tJ-pyrans) (1081, -(4H_-thiopyrans) ( 1 0 9 ) , and -(flavenes) ( 1 1 0 ) have been synthesized by reactions of tetraethyl 2-butene-1,4-diyldiphosphonate carbanions with aldehydes. 7 3 olefin synthesis. The phosphonate ( 1 1 2 1 , prepared from the methylenediphosphonate (111), provides a route to the tetraene (113), the C12-25 chiral fragment of the polyene macrolide anti- biotic pimaricin (Scheme 9 ) . 74 enamine (114) has been used to construct the phosphoryl-substituted 1-azadiene system ( 1 1 5 ) which, through intramolecular Diels-Alder reaction, provides a synthesis of functionalized quinolizidine

Not surprisingly the olefination is highly

Suitably substituted vinylphosphonates can be used in

Olefination with the diphosphonate

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8: YIides and Related Compounds 307

(107) n = 0, 1, 2

0 0 II II

( Et 01, PCH ,CH=CHCH, P(OE1 l2 t RKH= CHI, CHO

/ z Bu”~ i , - 78 ‘C

(111) (112)

1

R = Me0 L i - i i i 1 ed OR

(113 1

Reagents: i, H30+; i i , LOA; iii,

Scheme 9

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308 Organophosphorus Chemktry

' I HN(CH,), CH=CH,

(114 1 (EtO),P+o

I

(116) n = 3

(117) n = 4 Reagents: i , L D A ; i i , RCHO; iii, H 0 ; iv, A

2

Scheme 10

(117) and indolizidine (116) ring systems (Scheme 1 0 ) . 75

A wide variety of a-fluoroalkylphosphonates have been prepared by reaction of the carbanion of the fluoromethylphosphonate

0 ' II

( P ~ ' o ) , PCH,F

(118) 76 (118) with alkyl halides, acyl halides, aldehydes-and ketones.

Fluorinated a,B-unsaturated ketones ( 1 1 9 ) have been prepared in excellent yield and stereospecifically E, by phosphonate-based 01efination.~~ utilizing more vigorous conditions, PO-olefination has been extended to the synthesis of trisubstituted vinyl chlorides.

By reducing the bulk of the phosphonate ester and

78

A variety of phosphoryl-substituted sulphines ( 1 2 0 ) have been prepared by reaction of a-silyl phosphoryl-stabilized carbanions with sulphur dioxide.79 Treatment of (120) with lithium alkyls, followed by aldehydes offers a new route to a,~-unsaturated

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8: Ylides and Related Compounds 309

RF=CF3, C2F,, n-C,Fl,

0 0 R2 0 1 11 i , i i 1 II I ,o- 1 11 * RZP-C-SS, R2P-C=S=0 R 2PCHR2

SiMe, I SiMe, I. '0 A 2

R' = O(Alkyl1, Ph

4 Reagents: i , Bu"Li ; i i , SO2; iii, R L I ; ' IV, ' R CHO

(120)

i i i , i v I 0 II

R3'sTcHR4 (121)

Scheme 11

sulphoxides (121) (Scheme 11). The highly reactive, chiral dienophile ( 1 2 3 ) has been prepared by olefination of methyl glyoxylate with the phosphonate (122). Phosphonate-based olefination has been applied to the synthesis of a,8-unsaturated thioamides. 81 these reactions can be prepared by reaction of the carbanion of diethyl ethylphosphonate with alkyl or aryl isothiocyanate followed by hydrolysis.

intramolecular phosphonate-olefination include a synthesis of the

The a-phosphono thioamides ( 1 2 4 ) required for

Examples of cyclopentenone formation through the use of

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3 10 Organophosphorus Chemistry

h e

sesquiterpene quadrone (125 1. 82

(diazomethy1)phosphonate carbanion with dialkyl ketones having v-hydrogens gives moderate yields of cyclopentenes 2 the diazoalkene ( 1 2 6 ) and carbene insertion. 83

The reaction of dialkyl

A variety of B-keto phosphonates ( 1 2 7 ) have been prepared by reactions of the carbanion derived from dimethyl methyl- phosphonate with substituted carboxylic esters .84 of phosphonate carbanions with oxygen have been further in~estigated.~~

The reactions

The reaction generates a carbonyl group at the

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8: Ylides and Related Compounds 311

0 II

0 II

(MeO),P-eH2 + RCOOMe -L (MeO),PCH,COR

Li (129) (128) RL = Me, Ph, PhCH2,

MeS, EtS, COOLi

carbanion centre, e 3 . a-mercaptylalkylphosphonates (128) give the corresponding carboxylic acid thiol esters (129).

4 Selected Applications in Synthesis

Both the use of the Wittig reaction in the synthesis of natural products86 and its industrial application^^^ have been reviewed in a volume dedicated toGeorg Wittig.

4.1 Carbohydrates. - In a new route to (+)-exo-brevicomin from derivitized a-D-glucopyranoside, conversion of the aldehyde ( 1 3 0 ) to the alkene (131) is much more efficiently achieved by reaction

0 qHo -t (EtO),PCHCOMe II - BZO

--+ BrO

OTs

(130)

Bz = PhCO

TS = Tosyl

OTs

(131 1

with acetylmethylphosphonate carbanion than with acetylmethylene ylide.88 used to construct the side chain in the first synthesis of the antifungal antibiotic sinefungin. 89

The Wadsworth reaction of the phosphonate (132) has been

An intramolecular olefination

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3 12 Organophosphorus Chemistry

(132)

0 II

R’ o°CYp(oMe)2

COOMe

+ BJOOCNH ACH2 CHO

Mg(0MeI2 \ B ~ O O C N H

OR OR McOOC

PH

- K : D COOR’

of the phosphonate (133) is the key step in an enantiospecific synthesis of (-1-shikimic acid. 90

4.2 0-Lactams. - Intramolecular Wittig reactions have been used to form the pyrollidine ring in syntheses of 2-cyclopropyl-1-carbopen- 2-em- 3-carboxylic acids9’ and 2-aryl and 2-heteroaryl analogues (134) of thiena~nycin.~~ Phosphonate-based olefination has been used similarly to construct the dehydropiperidine ring in a synthesis of the a-hydroxy-1-carbacephem ( 1 3 5 ) . 93

Ylide intermediates (136) have been both implicated in and isolated from the tervalent phosphorus-induced carbonyl-carbonyl coupling route to penams. 94

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8: Ylides and Related Compounds 3 13

0 +NYPPh3 C O O R ~

OH PhOCH2CONH, H ' fi

600- Na'

(135)

- :md 0 I C O O R ~

(134) R = Ar, 0 #

H

LOOR'

(136) R4= NMe2 , OMe, OEt, OPh

4 .3 Leukotrienes and Related Compounds. - Among those compounds related to leukotrienes which have been synthesized by what are now largely standard Wittig methods are leukotrienes CqY D4,and

E4, [ 1 4 , 15-3H,] leukotriene E4 dimethyl ester!5 and 7,7-dimethyl- eicosa-(5Z,8Z)-dienoic acid (137) .96 using stereoselective z olefination of the ylide ( 1 3 8 ) followed by alkaline hydrolysis as the final step (Scheme 1 2 ) .97 synthesis of (5?,12S)-diHETE (LTBX) (142) using a Wittig reaction of the phosphorane ( 1 4 0 ) with the aldehyde (141) as the key step has been reported (attempts to use the alternative phosphonate- and sulphone-based olefin syntheses failed) . 98

formed in the reaction was the desired E_ alkene. The first total,

LTB5 (139) has been synthesized

The total

The major isomer

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314 Organophosphorus Chemistry

- PPh3 P - (138)

COOH

Scheme 12

( c H ~ ) ~ COOR'

( 1 4 0 )

+ R'oy:,c5"l, (141)

2 ( 1 4 2 ) R1 = R = H

stereospecific synthesis of (14S,l5S)-oxido (5Z,8Z,lOE,lZE)- eicosatetraenoic acid !144) has been achieved using a Wittig reaction of the ylide (143) as a final step.99 (146) and the hornologue (1471, possible LTA4 antagonists, have been synthesized from the aldehyde (145) by consecutive Wittig

Secoleukotriene

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8: Ylides and Related Compounds 3 15

- /(CH,), COOH

1 Ph,P--l

!jHll

O (CH,),COOR

( 1 4 6 ) n = 4

( 1 4 7 ) n = 3

reactions. loo

of LTB4. Now the analogous metabolites which would be derived from similar oxidation of LTD4 have been synthesized by Wittig reaction of the epoxyaldehyde ( 1 4 8 ) with a phosphorane containing the appropriate oxygen function to give (149) and (1501, followed by reaction of the epoxy group with thiopeptide and deprotection.

The Wittig reaction has been used to prepare (7R)- deuterioarachidonic acid (151 ) Io2 and (7R_)-deuterio-5,6-

w-Oxidation is a known metabolic route for breakdown

101

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316 Organophosphorus Chemistry

c x 4 ( C H z - (CH,),X 1 COOMe

(149) X = CH20CH2Ph

(150) X = COOMe

(151 1 (152 )

/-HC=C=CH, OHCCH, Ph,P (CH 2)20SiR3 -t

(153) I

HC=C = CHCH ZCH 2 COOH

C - , C 5 H 1 1

dehydroarachidonic acid (152I1O3 for use in metabolic studies. There have been several reports of syntheses of arachidonic acid analogues, e.g. the allene (154) from the phosphorane ( 1 5 3 ) . The ethanoarachidonic acids (155), (1561, and (157) have been

104 -

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8: Ylides and Related Compounds 317

Ph, P w (CH,) , C O W

(158) n = 0,1, 2

(155) n =o, = 2 R I I P 4 + C 5 H , ,

(156) n = 1, rn = 1

(157) n = 2 , rn = 0 (159) rn = 0,1, 2

(161 1 (160) n + rn = 3

prepared from suitably substituted cyclopropylcarboxaldehydes by reactions with phosphonium ylides ( 1 5 8 ) and ( 1 5 9 ) .Io5 Similar methods have been used to prepare di- and triethanoarachidonic acids (1601, (1611, and (162).’06 However, in each of these cases one cyclopropyl group was introduced using the new functionalized cyclopropylmethylene ylide (163). A Wittig reaction of the silylated propargylidene ylide (164) with the trans dialdehyde ( 1 6 5 ) has been used to prepare the diene-diyne ( 1 6 6 ) in a synthesis of 7,13-bridged arachidonic acid analogues. 107

4.4 Macrolides. - Phosphonate-based, and to a lesser extent ylide- based, intramolecular olefination has been increasingly used as

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3 18 Organophosphorus Chemistry

H

2 Ph3P=CHC=CSiMe3 + dCHO (164) ‘CHO

(165)

-78 OC

,SiMe3 \ c@ cc, \C,

SiMe3

(166)

O d

Me CHO

K2CO3, toluene,

-20 OC, 18 -crown -6 *

the cyclization step in the synthesis of macrolides, e.g. -. ( + ) - 3 - deoxyrosaranolidelo8 and ( - )-maysine. In the first syntheses of baccharin B5 and roridin E, the required E , Z macrocycle is obtained by cyclization of the phosphonate ( 1 6 7 ) ; attempts to use

110 the corresponding phosphonium salt gave mainly the g,! isomer. A new synthesis of macrocyclic lactones uses intramolecular Wittig reactions of the salts ( 1 6 8 ) and has been applied to the synthesis of ambrettolide ( 1 6 9 ) and recifeiolide. 111

Consecutive Wittig reactions with methoxycarbonylmethylene ylide have been used to achieve chain-elongation by f o u r carbon atoms in a synthesis of the diolide ( 1 7 0 1 , a model system for the antibiotic elaiophylin. In an improved synthesis of the cytochalasins, Stork has used the dienylphosphonate ( 1 7 1 ) to prepare the triene precursor ( 1 7 2 ) for construction of the

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8: Ylides and Related Compounds 3 19

11 3 macrocyclic ring.

4.5 Pheromones. - A new synthesis of a major pheromone component, (Z,Z)-3,13-octadecadien-l-yl acetate ( 1 7 3 1 , of Syiianthedon species uses Wittig reactions with ylides ( 1 7 4 ) and ( 1 7 5 ) to introduce the

0

R’ P ~ ~ & C H ~ C O O C R ’ R’ (cH~),CHO c r --+

(168) n = 7,9,11 R2

(169)

I

he

(170)

OSiR3

Me

(172) COOEt

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320 Organophosphorus Chemistry

Ph,P=CH(CH,),Me

(174)

- Z double bonds and is claimed to be more efficient than those previously reported. The nonadecatriene (177 1 , a pheromone component from Boarimia selenaria females, has been synthesized from the phosphonium ylide (176). 115

4.6 Prostaglandins. - The standard reactions of carbanion and ylide derived from the phosphonate (178) and phosphonium salt ( 1 7 9 1 , respectively, have been used to introduce the side-chains in

0 II

(MeO), PCH2CO(CH2)4 Me

(178) (179)

MeN A \ /

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8: Ylides and Related Compounds 32 1

syntheses of ~ 2 - e p i - p r o ~ t a g l a n d i n ~ ~ ~ ~ ( + )-9-deoxy-prostaglandin D2, ( f 1-11-deoxyprostaglandin E 2 , chemically stable prostacyclin analogues ester , IL9 and pyridino prostanoids. I 2 O analogue ( 1 8 1 ) has been prepared using Wittig reactions of the ylides ( 1 8 2 ) and (183) to construct the side-chains .Iz1 Wittig reactions of p-rnethoxybenzylidenerriphenylphenylphosphorane have been

[ e.g., (180) l ,IL8 9,11 -thiathromboxane A2 methyl The aromatic prostaglandin

COOH Me0

(181 1

used to prepare a number of upper chain aromatic-modified prostaglandins (184) from PGA2. 1 2 2

4.7 Steroids and Related Compounds. - In a synthesis of dehydro- oogoniol (185) (a female-activating hormone of the water mould Achlya) from progesterone the side chain has been constructed using a series of Wittig rea~ti0ns.l~~ (186) and 3-sulphinyl analogues of testosterone have been reported and use an intramolecular Wittig reaction to form ring A (Scheme 1 3 1 . l ~ ~ has been used to prepare the triene (1891, which through cyclization and modification provides (+)-androst-4-en-3-0ne-l?- carboxylic acid.125

The syntheses of 3-thia

A Wittig reaction of the ylide (187) with aldehyde (188)

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322 Organophosphorus Chemistry

‘ 2

ii, iii I

Reagents: i , Ph3P=CH i i , H30+; i i i , 8ut OK, OMSO 2

Scheme 13

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8: Ylides and Related Compounds 323

(187) (188)

PhCH,O

(189)

4.8 Miscellaneous Applications. - The masked aldehydic ylide ( 1 9 0 ) has heen developed as a new reagent for the homologation of carbonyl compounds and used in a synthesis of 7,8-didehydro- desmosterol. 126

R'

R2 T:"" H (191) R' = H, R 2 = CH,OH

(192) R' = CH20H, R2 = H

Phosphorus-based methods remain important in polyene synthesis. Standard Wittig methods have been used to prepare the highly mutagenic fecapentaene-12 ( 1 9 1 1 , produced by certain colonic bacteria, and its regioisorner ( 1 9 2 ) . 127 Spiroretinal ( 1 9 3 ) and related compounds have been synthesized using phosphonate-based

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324 Organophosphori~.~ Chemistry

R Ye + (Et0)Z PCH, C=CHCN

i - i i i \

Reagents: i, N a H , ii, DIBAH, H'; i i i , h.p.1.c

Scheme 14

olefination to construct the side chains (Scheme 14). The triene ( 1 9 5 ) has been prepared (for use in the synthesis of tetranic acid antibiotics) from a Wittig reaction of (194) with the

appropriate aldehyde, followed by isomerization of the 2 : 1 , E , Z : E , E mixture formed initially. A prohormone of the fungi Blakeslea trispora has been synthe~ized.'~' The key step, Wittig reaction of the ylide ( 1 9 7 ) , gave a high proportion of the desired isomer only when the carboxylate of (196) was used. However, confusion in the diagrams, stereochemistry,or numbering makes this part of the paper difficult to follow.

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8: Ylides and Related Compounds 325

0

CHO M e coo-

Me COOR

Phosphorus-based methods have been used in syntheses of pseudomonates and related compounds. The phosphonate ( 1 9 8 ) has been used to introduce the ester side chain in a synthesis of methyl deoxypseudomonate B c199 and a variety of pseudomonic acids [e.g.,(201)] have been prepared by Wittig reactions of the chiral ylide ( 2 0 0 ) .I3*

-

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326 Organophosphorus Chemistry

OHCCHO \

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8: Ylides and Related Compounds 327

A s might be expected,reaction of the tetrakis(ylide1 with gaseous formaldehyde gives 1,4,5,8-tetravinylbiphenylene ( 2 0 3 ) ; however, a similar reaction with glyoxal forms a complex mixture from which the unstable antiaromatic polycycle ' ( 2 0 4 ) can be obtained in very low yield. 133 Low yields were also obtained from the three- fold Wittig reaction of the aldehydic phosphonium salt ( 2 0 5 ) to give the cyclophane (206).

( 2 0 2 )

134

20-Methyl and 20-cyano isobacteriochlorins, important compounds in relation to biosynthetic studies on vitamin B12, have been synthesized using a Wittig reaction of the ylide (207) with the monothioimide ( 2 0 8 ) to generate the A-D ring system.135 intramolecular Wittig reaction of the phosphonium salt (209) has been used as the key step in a simple synthesis of acamelin ( 2 1 0 ) , an allergy-inducing constituent of Australian blackwood.

An

136

In a synthesis of marine sponge components the alkyl side- chain was constructed by a Wittig reaction of the salt (2111, after attempts to use copper coupling reactions had failed. 13' The ylide ( 2 1 2 ) has been used in a synthesis of (+I-dihydropalustrine.

Full details have appeared of the use of chloromethyl-

138

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328 Organophosphorus Chemistry

C N (207) (208) \

+ CH,PPh, Br-

* Et3 N

Me0 OCOMe M e 0

OCOMe OCOMe

0

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8: Ylides and Related Compounds 329

+ Ph3P(CH2 ),,COOMe Br-

(211)

phosphinate-ylide (213) to prepare phosphonate-phosphinate analogues

[ (e_ ,g . , (214) 1 of p h o s p h ~ l i p i d s l ~ ~ (Scheme 15).

0 II 0

I1 I I OPh OPh

RHC=CHPCHZCI Ph 3P=CH-PCH,CI A

ii, iii I ( 2 1 3 )

R = C,8H3,0CH, CH - '1 8 H37

I 8 A

RCH CHZPCH2P(OEt), I

OPh

Reagents: i, RCHO; ii, (EtO)3P; iii, H,, Pd/C

Scheme 15

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330 Organophosphorus Chemistry

R e f e r e n c e s

1.

2. 3.

4 .

5 . 6 .

7. 8. 9 .

1 0 .

1 1 .

1 2 . 1 3 . 1 4 . 15.

16. 17 .

18. 19 . 20.

21 .

22.

23 . 24. 25 . 26 .

27. 28.

29.

30. 31. 32.

33.

34 .

35. 36. 37. 38. 39 . 40 . 41 .

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-

-

~

~

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8: Ylides and Related Compounds 33 1

42.

43. 44. 45. 46. 47.

48. 49. 50.

51.

52.

53. 54. 55. 56.

57. 58. 59. 60. 61. 62. 63. 64.

65.

66.

67.

68. 69. 70.

71.

72.

73.

74. 75. 76. 77. 78. 79.

80. 81. 82.

83.

84. 85.

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g, 1111.

-

________

K.-C. Tang and J.K. Coward, J. Org. Chem., 1983, 48, 5001. M. Mikolajczyk, W. Mindura, and S. Grzejszczak, Tzrahedron Lett., 1984, 25, 2489.

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332

86. 87. 88. 89.

90.

91.

92.

93.

94.

95.

96.

97. 98. 99.

100. 101.

102. 103.

104.

105.

106.

107. 108. 109.

110.

111. 112. 113. 114.

115.

116. 117. 118.

119. 120. 121.

122.

123.

Organophosphorus Chemistry

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