enantioselective synthesis of 3-fluoro-3-allyl-oxindoles via phos … · 2015. 5. 14. · 3 bn(6c)...

SUPPORTING INFORMATION

Enantioselective Synthesis of 3-Fluoro-3-allyl-oxindoles via Phos-phine-Catalyzed Asymmetric -addition of 3-Fluoro-Oxindoles to

2,3-Butadienoates

Tianli Wang, Ding Long Hoon, and Yixin Lu*

Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543

E-mail: [email protected]

1. General Information -------------------------------------------------------------------------------------------1

2. Optimization of Reaction Conditions ------------------------------------------------------------------------3

3. Proposed Reaction Cycle -------------------------------------------------------------------------------------6

4. Preparation of 3-Fluoro-substituted Oxindoles ---------------------------------------------------------8

5. Representative Procedure for -Addition of 3-Fluorinated Oxindoles ----------------------------------9

6. Asymmetric Synthesis of Chiral 3-Fluoro-3-allyl Oxindole Derivatives -----------------------------23

7. References-------------------------------------------------------------------------------------------------------24

8. NMR Spectra of the Products---------------------------------------------------------------------------------25

Electronic Supplementary Material (ESI) for ChemComm.This journal is © The Royal Society of Chemistry 2015

1. General Information

All the starting materials were obtained from commercial sources and used without further

purification unless otherwise noted. 1H and 13C NMR spectra were recorded at ambient temperature in

CDCl3 or D2O on a Bruker ACF300 or AMX500 (500 MHz) spectrometer. The chemical shifts are

reported in parts permillion (ppm) relative to CDC3 (δ = 7.26) for 1H-NMR and relative to the central

resonances of CDCl3 (δ = 77.0) for 13C-NMR. Multiplicity was indicated as follows: s (singlet), d

(doublet), t (triplet), q (quartet), m (multiplet), dd (doublet of doublet), br s (broad singlet). Coupling

constants (J) were reported in Hertz (Hz). Low resolution mass spectra were obtained on a

Finnigan/MAT LCQ pectrometer in ESI mode, and a Finnigan/MAT 95–T mass spectrometer in FAB

mode. All high resolution mass spectra were obtained on a Finnigan/MAT 95XL–T spectrometer. For

thin layer chromatography (TLC), Merck pre-coated TLC plates (Merck 60 F254) were used, and

compounds were visualized with a UV light at 254 nm. Further visualization was achieved by staining

with iodine, or ceric ammonium molybdate followed by heating on a hot plate. Flash chromatographic

separations were performed on 200-300 mesh silica gel. Enantiomeric excess was determined by HPLC

analysis using chiral column described below in detail. Optical rotations were measured with

polarimeter.

All the chiral phosphine catalysts were prepared by following our previously reported procedures.[1]

All the 3-fluoro-substituted oxindoles were synthesized based on known methods reported in

literature.[2]

The absolute configuration of 7a1 was assigned by comparing optical rotation of the corresponding

derivative 9 (Scheme S3) with the value reported in the literature,[3] and the configuration of other

-addition products were assigned by analogy.

2. Optimization of Reaction Conditions

R

NH

PPh2

NH

PPh2

OTBDPS

O

NHBoc

HN

PPh2

HN

S

F1d

O

F3C CF3

2a: R = Me2b: R = i-Pr2c: R = t-Bu

NH

PPh2

O

F3C CF3

2d

OH

3

NH

PPh2

OTBDPS

O

NHBoc

NHR

PPh2

1a: R = Boc1b: R = Ts

NH

PPh2

1c

O

4

NH

PPh2

O

F3C CF3

2e: R = TMS, 2f: R = TBS2g: R = TBDPS

OR

Scheme S1: Chiral phosphine catalysts used in this study. (TBDPS = tert-butyldiphenylsilyl, TBS = tert-butyldimethylsilyl, TMS = trimethylsilyl, Ts = 4-toluenesulfonyl)

A. Optimization of conditions for ‐Addition of 3‐fluoro‐oxindoles

Table S1: Asymmetric -addition of 3-fluoro-oxindole 5a with allenoate 6c catalyzed by different

chiral phosphines in toluene [a]

Entry Cat. R(5a) t [h] Yield [%][b] ee [%][c]

1 1a Boc(5a1) 1 88 32

2 1b Boc(5a1) 0.5 95 55

3 1c Boc(5a1) 1 88 41

4 1d Boc(5a1) 0.5 98 77

5 2a Boc(5a1) 1 95 90

6 2b Boc(5a1) 1 93 90

7 2c Boc(5a1) 2 88 88

8 2d Boc(5a1) 2 89 64

9 2e Boc(5a1) 2 93 93

10 2f Boc(5a1) 2 92 92

11 2g Boc(5a1) 2 95 93

12 3 Boc(5a1) 2 90 6

13 4 Boc(5a1) 2 90 -9

14 2g Cbz(5a2) 2 86 93

15 2g Ac(5a3) 4 82 83

16 2g Me(5a4) 4 <5 --

[a] Reactions were performed with 5a (0.05 mmol), 6c (0.06 mmol) and catalyst (0.005 mmol) in toluene (0.5 mL) at

room temperature. [b] Yields of isolated products. [c] Determined by HPLC analysis on a chiral stationary phase.

Table S2: Asymmetric -addition of 3-fluoro-oxindole (5a1) with different allenoates (6) catalyzed by

phosphine catalyst 2g in toluene [a]

Entry R (6) 7 Yield [%][b] ee [%][c]

1 Me(6a) 7a1-1 92 91

2 t-Bu(6b) 7a1-2 90 91

3 Bn(6c) 7a1-3 95 93

4 6d 7a1-4 91 93

5 6e 7a1-5 92 93

6 6f 7a1-6 89 92

7 6g 7a1-7 85 86

8 Ph(6h) 7a1-8 88 77

[a] Reaction conditions: 5a1 (0.05 mmol), 6 (0.06 mmol), and the catalyst 2g (0.005 mmol) in toluene (0.5 mL). [b]

Yields of isolated products. [c] Determined by HPLC analysis on a chiral stationary phase.

Table S3: Asymmetric -addition oxindole 5a1 with allenoate 6c catalyzed by 2g: optimizing the

solvents and other reaction conditions [a]

Entry Solvent T [oC] t [h] Yield [%][b] ee [%][c]

1 toluene RT 2 95 93

2 xylene RT 2 95 90

3 Et2O RT 2 88 73

4 CHCl3 RT 4 90 88

5 CH2Cl2 RT 4 92 92

6 EA RT 6 81 45

7 toluene 0 12 83 69

[a] Reaction conditions: 5a1 (0.05 mmol), 6c (0.06 mmol), and the catalyst 2g (0.005 mmol) in solvent (0.5 mL). [b]

Yields of isolated products. [c] Determined by HPLC analysis on a chiral stationary phase.

Scheme S2: Reactions of -substituted and -substituted allenoates (6i and 6j) with

N-Boc-3-fluoro-oxindole (5a1) by catalyst 2g.

3. Proposed Reaction Cycle

= PR3•

CO2Bn

PR3

CO2Bn

H-shiftPR3

CO2Bn

NO

Boc

F

NO

Boc

F

NO

Boc

CO2Bn

PR3

F

NO

Boc

CO2Bn

PR3

F

NO

Boc

CO2Bn

F NH

PPh2

O

F3C CF3

OTBDPS

Figure S1: Proposed catalytic cycle.

Figure S2. Proposed transition-state model.

Table S4. Asymmetric -addition promoted by different phosphine catalysts: investigating the H-bonding effect.[a]

cat. (10 mol%)

toluene, RTNO

NO

6c

7a1: R = Boc7a': R = H

•CO2Bn

+

5a1: R = Boc; 5a': R = H

CO2Bn

RR

FF

N

PPh2

O

F3C CF3

2g: R = H2g': R = Me

R

OTBDPS

Entry Sub. Cat. t [h] 7/Yield [%][b] ee [%][c]

1 5a1 2g 2 7a/95 93

2 5a1 2g’ 4 7a/85 37

3 5a’ 2g 2 7a’/81 43

[a] Reaction conditions: substrate (0.05 mmol), 6c (0.06 mmol), and catalyst (0.005 mmol) in toluene (0.5 mL) at room terature. [b] Isolated yield. [c] Determined by HPLC analysis on a chiral stationary phase.

4. Preparation of the 3-fluoro-substituted oxindoles

General procedure for preparing 3-fluoro-substituted oxindoles 5:[2]

All 3-fluoro-substituted oxindoles 5 were prepared from compounds 5-1 via known fluorination

using NFSI as F-source following literature procedure (16-48% yields).[2] Substrates 5a-c and 5f-h are

known compounds, and their characterization data were in agreement with those reported in the

literature.[2] Unknown compounds 5d, 5e and 5a’ were fully characterized.

tert-Butyl 6-bromo-3-fluoro-2-oxoindoline-1-carboxylate (5d)

A white sold; 1H NMR (500 MHz, CDCl3) δ 8.13 (s, 1H), 7.40-7.35 (m, 2H), 5.70 (d, J = 51.1 Hz, 1H),

1.64 (s, 9H); 13C NMR (125 MHz, CDCl3) δ 168.34 (d, J = 18.2 Hz), 148.40, 141.89 (d, J = 4.6 Hz),

128.14 (d, J = 2.7 Hz), 127.08, 125.81 (d, J = 3.6 Hz), 119.23, 85.62, 85.23 (d, J = 189.5 Hz), 27.99; 19F

NMR (282.38 MHz, CDCl3) δ -187.10 (d, J = 51.5 Hz); HRMS (ESI) m/z calcd C13H13BrFNNaO3

[M+Na]+ = 351.9955, found = 351.9950.

tert-Butyl 3-fluoro-2-oxo-5-(trifluoromethyl)indoline-1-carboxylate (5e)

A white sold; 1H NMR (500 MHz, CDCl3) δ 7.95 (d, J = 8.8 Hz, 1H), 7.39 (s, 1H), 7.31 (d, J = 8.9 Hz,

1H), 5.71 (d, J = 50.4 Hz, 1H), 1.63 (s, 9H); 13C NMR (125 MHz, CDCl3) δ 168.17 (d, J = 17.3 Hz)

148.45, 146.10, 139.35 (d, J = 4.6 Hz), 124.61, 123.15 (d, J = 17.3 Hz), 121.43, 119.24 (d, J = 32.8 Hz),

116.99, 85.54, 85.19 (d, J = 190.4 Hz), 27.98; 19F NMR (282.38 MHz, CDCl3) δ -58.28, -188.44 (d, J =

50.5 Hz); HRMS (ESI) m/z calcd C14H13F4NNaO3 [M+Na]+ = 342.0729, found = 342.0720.

3-Fluoroindolin-2-one (5a’)

NH

O

F

5a'

A white sold; 1H NMR (500 MHz, CDCl3) δ 9.07 (s, 1H), 7.45 (d, J = 7.6 Hz, 1H), 7.34 (t, J = 7.6 Hz, 1H),

7.09 (t, J = 7.6 Hz, 1H), 6.94 (d, J = 8.2 Hz, 1H), 5.74 (d, J = 51.1 Hz, 1H); 13C NMR (125 MHz, CDCl3)

δ 173.87 (d, J = 18.2 Hz), 141.96 (d, J = 5.5 Hz), 131.51 (d, J = 2.7 Hz), 126.27, 123.32 (d, J = 2.7 Hz),

123.26 (d, J = 16.4 Hz), 110.90, 86.67 (d, J = 188.6 Hz); 19F NMR (282.38 MHz, CDCl3) δ -193.68 (d, J

= 50.5 Hz); HRMS (ESI) m/z calcd C8H6FNNaO [M+H]+ = 174.0331, found = 174.0229.

5. Representative Procedure for -Addition of 3-Fluorinated Oxindoles

To dried schlenk tube equipped with a stirrer bar were added 3-fluoro-oxindole 5a1 (12.5 mg, 0.05 mmol)

and catalyst 2g (3.8 mg, 0.005 mmol), followed by the addition of dry toluene (0.5 mL). Allenoate 6c

(10.5 mg, 0.06 mmol) was slowly added via syringe, and the reaction mixture was stirred at room

temperature for 2 h. Then, the solvent of toluene was removed under reduced pressure, and the residue

was purified by column chromatography on silica gel (hexane/ethyl acetate = 15:1) to afford 7a1 (20.3

mg, 95% yield) as a white foam.

(R,E)-tert-Butyl 3-(4-(benzyloxy)-4-oxobut-2-enyl)-3-fluoro-2-oxoindoline-1-carboxylate (7a1)

NBoc

O

F

COOBn

7a1

A white foam; []25D = +25.5 (c 0.40, CHCl3);

1H NMR (500 MHz, CDCl3) δ 7.91 (d, J = 8.2 Hz, 1H),

7.47-7.41 (m, 2H), 7.38-7.31 (m, 5H), 7.22 (d, J = 7.6 Hz, 1H), 6.90-6.83 (m, 1H), 5.97 (d, J = 15.8 Hz,

1H), 5.17 (s, 2H), 3.15-3.09 (m, 1H), 2.97-2.88 (m, 1H), 1.63 (s, 9H); 13C NMR (125 MHz, CDCl3) δ

170.01 (d, J = 21.0 Hz), 165.25, 148.51, 140.11 (d, J = 4.6 Hz), 138.78 (d, J = 7.3 Hz), 135.74, 131.83

(d, J = 3.6 Hz), 128.53, 128.23, 128.12, 126.71, 125.09 (d, J = 2.7 Hz), 124.86, 123.92 (d, J = 19.1 Hz),

115.72, 91.69 (d, J = 189.5 Hz), 85.19, 66.31, 38.34 (d, J = 30.1 Hz), 27.98; 19F NMR (282.38 MHz,

CDCl3) δ -149.02 (dd, J1,2 = 12.4 Hz, J1,3 = 18.6 Hz); HRMS (ESI) m/z calcd for C24H24FNNaO5

[M+Na]+ = 448.1531, found = 448.1543; The ee value was 93%, tR (major) = 25.3 min, tR (minor) = 22.4

min (Chiralcel IE, λ = 254 nm, 5% i-PrOH/hexanes, flow rate = 1.0 mL/min).

Racemic 7a

Enantiomerically enriched 7a

(R,E)-tert-Butyl 3-(4-(benzyloxy)-4-oxobut-2-enyl)-5-chloro-3-fluoro-2-oxoindoline-

1-carboxylate (7b)

NBoc

O

F

COOBnCl

7b



7.43 (dt, J1,2 = 1.9 Hz, J1,3 = 8.9 Hz, 1H), 7.40-7.37 (m, 1H), 7.35-7.31 (m, 5H), 6.84-6.78 (m, 1H),

5.98 (d, J = 15.8 Hz, 1H), 5.17 (s, 2H), 3.12-3.05 (m, 1H), 2.98-2.90 (m, 1H), 1.62 (s, 9H); 13C NMR

(125 MHz, CDCl3) δ 169.33 (d, J = 21.0 Hz), 165.12, 148.34, 138.63 (d, J = 5.5 Hz), 138.00 (d, J = 7.4

Hz), 135.70, 131.87 (d, J = 2.7 Hz), 130.73 (d, J = 2.7 Hz), 128.58, 128.28, 128.15, 127.13, 125.54 (d,

J = 19.1 Hz), 125.01, 117.15, 91.34 (d, J = 191.3 Hz), 85.60, 66.42, 38.23 (d, J = 29.2 Hz), 27.97; 19F

NMR (282.38 MHz, CDCl3) δ -149.61 (t, J = 14.4 Hz); HRMS (ESI) m/z calcd for C24H23FClNNaO5



Racemic 7b

Enantiomerically enriched 7b

(R,E)-tert-Butyl 3-(4-(benzyloxy)-4-oxobut-2-enyl)-6-chloro-3-fluoro-2-oxoindoline-

1-carboxylate (7c)

NBoc

O

F

COOBn

7c

Cl


1H NMR (500 MHz, CDCl3) δ 7.99 (s, 1H), 7.38-7.32 (m,

6H), 7.21 (dd, J1,2 = 1.3 Hz, J1,3 = 8.2 Hz, 1H), 6.86-6.80 (m, 1H), 5.98 (d, J = 15.1 Hz, 1H), 5.17 (s,

2H), 3.14-3.07 (m, 1H), 2.94-2.85 (m, 1H), 1.63 (s, 9H); 13C NMR (125 MHz, CDCl3) δ 169.57 (d, J =

21.0 Hz), 165.17, 148.27, 141.06 (d, J = 5.5 Hz), 138.23 (d, J = 7.3 Hz), 137.87 (d, J = 3.7 Hz), 135.67,

128.58, 128.31, 128.19, 127.02, 125.82, 125.28 (d, J = 2.8 Hz), 122.08, 116.60, 91.27 (d, J = 190.5

Hz), 85.78, 66.43, 38.21 (d, J = 29.2 Hz), 27.95; 19F NMR (282.38 MHz, CDCl3) δ -148.82 (dd, J1,2 =

12.4 Hz, J1,3 = 19.6 Hz); HRMS (ESI) m/z calcd for C24H23FClNNaO5 [M+Na]+ = 482.1141, found =

482.1147; The ee value was 94%, tR (major) = 15.3 min, tR (minor) = 13.7 min (Chiralcel IE, λ = 254 nm,

5% i-PrOH/hexanes, flow rate = 1.0 mL/min).

Racemic 7c

Enantiomerically enriched 7c

(R,E)-tert-Butyl 3-(4-(benzyloxy)-4-oxobut-2-enyl)-6-bromo-3-fluoro-2-oxoindoline-

1-carboxylate (7d)

NBoc

O

F

COOBn

Br

7d


1H NMR (500 MHz, CDCl3) δ 8.16 (s, 1H), 7.39-7.33 (m,

7H), 6.85-6.79 (m, 1H), 5.98 (d, J = 15.8 Hz, 1H), 5.17 (s, 2H), 3.13-3.06 (m, 1H), 2.93-2.85 (m, 1H),

1.63 (s, 9H); 13C NMR (125 MHz, CDCl3) δ 169.50 (d, J = 21.0 Hz), 165.17, 148.29, 141.09 (d, J = 4.6

Hz), 138.27 (d, J = 7.3 Hz), 135.69, 128.60 (d, J = 12.8 Hz), 128.33, 128.20, 128.02, 127.85, 127.07,

126.06, 122.75 (d, J = 19.1 Hz), 119.39, 91.33 (d, J = 190.4 Hz), 85.80, 66.44, 38.18 (d, J = 29.2 Hz),

27.97; 19F NMR (282.38 MHz, CDCl3) δ -149.24 (dd, J1,2 = 12.4 Hz, J1,3 = 19.6 Hz); HRMS (ESI) m/z

calcd for C24H23BrFNNaO5 [M+Na]+ = 526.0636, found = 526.0645; The ee value was 94%, tR (major) =

15.8 min, tR (minor) = 14.1 min (Chiralcel IE, λ = 254 nm, 5% i-PrOH/hexanes, flow rate = 1.0 mL/min).

Racemic 7d

Enantiomerically enriched 7d

(R,E)-tert-Butyl 3-(4-(benzyloxy)-4-oxobut-2-enyl)-3-fluoro-2-oxo-5-(trifluoromethyl)indoline-

1-carboxylate (7e)

NBoc

O

F

COOBnF3C

7e



7.37-7.31 (m, 6H), 7.27 (d, J = 8.2 Hz, 1H), 6.87-6.81 (m, 1H), 5.99 (d, J = 15.8 Hz, 1H), 5.17 (s, 2H),

3.15-3.08 (m, 1H), 2.95-2.86 (m, 1H), 1.63 (s, 9H); 13C NMR (125 MHz, CDCl3) δ 169.44 (d, J = 21.0

Hz), 165.06, 148.34, 146.07, 138.55 (d, J = 5.5 Hz), 137.87 (d, J = 6.4 Hz), 135.69, 128.57, 128.29 (d,

J = 16.2 Hz), 127.32, 125.45 (d, J = 19.1 Hz), 124.68, 121.40, 119.35, 118.16, 117.18, 91.30 (d, J =

192.2 Hz), 85.73, 66.45, 38.32 (d, J = 29.2 Hz), 27.97; 19F NMR (282.38 MHz, CDCl3) δ -58.28,

-150.80 (dd, J1,2 = 13.4 Hz, J1,3 = 20.6 Hz); HRMS (ESI) m/z calcd for C25H23F4NKO5 [M+K]+ =

532.1149, found = 532.1143; The ee value was 92%, tR (major) = 8.8 min, tR (minor) = 8.2 min

(Chiralcel IE, λ = 254 nm, 5% i-PrOH/hexanes, flow rate = 1.0 mL/min).

Racemic 7e

Enantiomerically enriched 7e

(R,E)-tert-Butyl 3-(4-(benzyloxy)-4-oxobut-2-enyl)-3-fluoro-5-methyl-2-oxoindoline-

1-carboxylate (7f)

NBoc

O

F

COOBnMe

7f



7.38-7.31 (m, 5H), 7.25-7.21 (m, 2H), 6.86-6.80 (m, 1H), 5.99 (d, J = 15.5 Hz, 1H), 5.17 (s, 2H),

3.12-3.05 (m, 1H), 2.97-2.91 (m, 1H), 2.35 (s, 3H), 1.62 (s, 9H); 13C NMR (125 MHz, CDCl3) δ 170.26

(d, J = 21.0 Hz), 165.31, 148.59, 138.91 (d, J = 7.3 Hz), 137.76 (d, J = 5.5 Hz), 135.79, 134.97 (d, J =

2.7 Hz), 132.35 (d, J = 2.7 Hz), 128.56, 128.26, 128.13, 126.63, 125.27, 123.86 (d, J = 18.2 Hz),

115.55, 91.86 (d, J = 189.5 Hz), 85.02, 66.31, 38.36 (d, J = 30.1 Hz), 28.02, 20.98; 19F NMR (282.38

MHz, CDCl3) δ -148.47 (dd, J1,2 = 13.4 Hz, J1,3 = 18.6 Hz); HRMS (ESI) m/z calcd for C25H26FNNaO5



Racemic 7f

Enantiomerically enriched 7f

(R,E)-tert-Butyl 3-(4-(benzyloxy)-4-oxobut-2-enyl)-3-fluoro-5-methoxy-2-oxoindoline-1-

carboxylate (7g)

NBoc

O

F

COOBnMeO

7g



7.38-7.31 (m, 5H), 6.98-6.94 (m, 2H), 6.88-6.82 (m, 1H), 5.99 (d, J = 15.8 Hz, 1H), 5.16 (s, 2H), 3.77

(s, 3H), 3.13-3.06 (m, 1H), 2.95-2.86 (m, 1H), 1.62 (s, 9H); 13C NMR (125 MHz, CDCl3) δ 170.19 (d, J

= 21.0 Hz), 165.25, 157.15 (d, J = 2.7 Hz), 148.61, 138.75 (d, J = 7.3 Hz), 135.76, 133.24 (d, J = 5.5

Hz), 128.56, 128.27 (d, J = 10.9 Hz), 126.79, 124.97 (d, J = 18.2 Hz), 117.02, 117.00, 116.88, 110.46,

91.92 (d, J = 190.5 Hz), 84.99, 66.34, 55.67, 38.42 (d, J = 29.2 Hz), 28.03; 19F NMR (282.38 MHz,

CDCl3) δ -149.56 (dd, J1,2 = 14.4 Hz, J1,3 = 19.6 Hz); HRMS (ESI) m/z calcd for C25H26FNNaO6



Racemic 7g

Enantiomerically enriched 7g

(R,E)-tert-Butyl

3-(4-(benzyloxy)-4-oxobut-2-enyl)-3-fluoro-5,7-dimethyl-2-oxoindoline-1-carboxylate (7h)

NBoc

O

F

COOBnMe

Me

7h


1H NMR (500 MHz, CDCl3) δ 7.37-7.32 (m, 5H), 7.05 (s,

2H), 6.85-6.79 (m, 1H), 5.97 (d, J = 15.8 Hz, 1H), 5.16 (s, 2H), 3.08-3.01 (m, 1H), 2.97-2.88 (m, 1H),

2.31 (s, 1H), 2.19 (s, 1H), 1.60 (s, 9H); 13C NMR (125 MHz, CDCl3) δ 171.25 (d, J = 21.0 Hz), 165.29,

148.41, 139.05 (d, J = 7.3 Hz), 136.14 (d, J = 5.5 Hz), 135.86, 135.28 (d, J = 3.7 Hz), 134.96 (d, J =

2.7 Hz), 128.54, 128.21, 128.11, 126.50, 125.26 (d, J = 18.2 Hz), 124.55, 122.79, 92.61 (d, J = 190.4

Hz), 85.28, 66.26, 38.57 (d, J = 30.1 Hz), 27.76, 20.85, 19.48; 19F NMR (282.38 MHz, CDCl3) δ

-149.29 (t, J = 12.4 Hz); HRMS (ESI) m/z calcd for C26H28FNNaO5 [M+Na]+ = 476.1844, found =

476.1858; The ee value was 90%, tR (major) = 22.2 min, tR (minor) = 19.1 min (Chiralcel IE, λ = 254 nm,

5% i-PrOH/hexanes, flow rate = 1.0 mL/min).

Racemic 7h

Enantiomerically enriched 7h

(R,E)- Benzyl 4-(3-fluoro-2-oxoindolin-3-yl)but-2-enoate (7a’)

NH

O

F

COOBn

7a'



7.38-7.32 (m, 5H), 7.13 (t, J = 7.6 Hz, 1H), 6.97 (dt, J1,2 = 4.4 Hz, J1,3 = 15.8 Hz, 1H), 6.75 (d, J = 8.2

Hz, 1H), 5.97 (dt, J1,2 = 1.9 Hz, J1,3 = 15.8 Hz, 1H), 5.78 (d, J = 51.1 Hz, 1H), 5.16 (s, 2H), 4.55-4.50

(m, 1H), 4.42-4.37 (m, 1H); 13C NMR (125 MHz, CDCl3) δ 170.85 (d, J = 18.2 Hz), 165.17, 143.26 (d,

J = 4.6 Hz), 140.53, 135.53, 131.58 (d, J = 2.7 Hz), 128.60, 128.40 (d, J = 2.7 Hz), 126.40, 123.67 (d,

J = 2.7 Hz), 123.10, 122.75 (d, J = 16.4 Hz), 109.28, 85.97 (d, J = 188.6 Hz), 66.63, 40.62; 19F NMR

(282.38 MHz, CDCl3) δ -192.47 (d, J = 50.5 Hz); HRMS (ESI) m/z calcd for C19H16FNNaO3 [M+Na]+

= 348.1012, found = 348.1017; The ee value was 43%, tR (major) = 32.5 min, tR (minor) = 24.5 min

(Chiralcel IE, λ = 254 nm, 40% i-PrOH/hexanes, flow rate = 1.0 mL/min).

Racemic 7a’

Enantiomerically enriched 7a’

6. Asymmetric Synthesis of Chiral 3-Fluoro-3-allyl Oxindole Derivatives

i) O3, DCM, - 78 oC

ii) Me3P=CH2, THF, 0 - RTNBoc

O

F CO2Bn

7a1

NBoc

O

F

8

Pd/C, H2

EA, 0 oC, 10 min

(76 % for two steps) (91%)NBoc

O

F

9

Found: []D25 = +15.5 (c 0.46 CHCl3)

Reported [3]: (R)-9 with 91% ee

[]D20 = +12.9 (c 1.09 CHCl3)

Scheme S3: Syntheis chiral 3-fluoro-3-allyl oxindole and its derivatives.

(R)-tert-Butyl 3-allyl-3-fluoro-2-oxoindoline-1-carboxylate (8)

NBoc

O

F

8

To a solution of 7a1 (85 mg, 0.20 mmol) in CH2Cl2 (3.0 mL) at -78 oC, O3 was bubbled until the

reaction was complete (monitored by TLC). Ph3P was added to quench the reaction at -78 oC, and then

kept stirring for another 10 min. The reaction mixture was warmed to room temperature and passed

through a short pad of silica gel, and eluted with EtOAc. The filtrate was concentrated and the residue

was purified by flash column chromatography on silical gel (hexane/ethyl acetate = 5:1) to afford the

corresponding aldehyde as a white foam, which was used directly in the next step.

To a solution of methyltrimethylphosphonium iodide (54 mg, 0.30 mmol) in dry THF (3.0 mL) at -78 oC, n-BuLi (133 µL, 2.0 M in hexane, 0.30 mmol) was slowly added and the mixture was kept stirring

at -78 oC for 1 h. Then, the mixture was warmed to 0 oC and stirred for another 1 h. The above crude

aldehyde in dry THF (2.0 mL) was introduced dropwise, and the resulting mixture was stirred at 0 oC

until the reaction was completed (monitored by TLC). The reaction mixture was filtrated by a short

pad of silica gel, and eluted with CH2Cl2. The filtrate was concentrated and the residue was purified by

flash column chromatography (hexane/ethyl acetate = 20:1) to afford pure compound 8 as a white

foam-oil (44.1 mg, 76% total yield). []25D = +13.5 (c 0.22, CHCl3);

1H NMR (500 MHz, CDCl3) δ

7.89 (d, J = 8.2 Hz, 1H), 7.47-7.41 (m, 2H), 7.22 (t, J = 7.6 Hz, 1H), 5.60-5.53 (m, 1H), 5.16 (d, J =

6.3 Hz, 1H), 5.13 (s, 1H), 3.01-2.94 (m, 1H), 2.88-2.80 (m, 1H), 1.64 (s, 9H); 13C NMR (125 MHz,

CDCl3) δ 170.78 (d, J = 21.0 Hz), 148.71, 140.21 (d, J = 4.6 Hz), 131.40 (d, J = 2.7 Hz), 128.44 (d, J =

8.2 Hz), 124.84, 124.68, 124.52, 121.50, 115.47, 92.50 (d, J = 188.6 Hz), 84.93, 40.06 (d, J = 28.2 Hz),

28.04; 19F NMR (282.38 MHz, CDCl3) δ -149.45 (dd, J1,2 = 11.4 Hz, J1,3 = 16.5 Hz); HRMS (ESI) m/z

calcd for C16H18FNNaO3 [M+Na]+ = 314.1170, found = 314.1168.

(R)-tert-Butyl 3-fluoro-2-oxo-3-propylindoline-1-carboxylate (9)

To a mixture of compound 8 (29 mg, 0.10 mmol) and 10% Pd/C (3 mg) in EtOAc (1.0 mL) at 0 oC, H2

was bubbled about 5 min, and the TLC shows that the reaction is completed. The catalyst Pd/C was

removed by filtration. The filtrate was concentrated and further purified by flash column

chromatography (hexane/ethyl acetate = 20:1) to give the known compound 9 as a white foam-solid

(26.5 mg, 91% yield). []25D = +15.5 (c 0.46, CHCl3);

1H NMR (500 MHz, CDCl3) δ 7.90 (d, J = 8.8

Hz, 1H), 7.44-7.41 (m, 2H), 7.23 (t, J = 7.6 Hz, 1H), 2.23-2.07 (m, 2H), 1.64 (s, 9H), 1.33-1.25 (m,

1H), 1.21-1.13 (m, 1H), 0.90 (t, J = 7.6 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 171.41 (d, J = 21.9

Hz), 148.81, 140.29 (d, J = 5.5 Hz), 131.27 (d, J = 2.7 Hz), 125.28 (d, J = 19.1 Hz), 124.95 (d, J = 2.7

Hz), 124.42, 115.50, 93.57 (d, J = 184.9 Hz), 84.90, 37.80 (d, J = 27.3 Hz), 28.05, 16.15 (d, J = 6.4

Hz), 13.95; 19F NMR (282.38 MHz, CDCl3) δ -148.30 (t, J = 13.4 Hz).

(R)-9 was reported in literature[3]: 91% ee, []20D = +12.9 (c 1.09, CHCl3). The above obtained

compound 9 was found to have an []25D = +15.5 (c 0.46, CHCl3). Therefore, the absolute

configuration of oxindole 7a1 was deduced to be R.

7. References

[1] (a) X. Han, Y. Wang, F. Zhong, Y. Lu, J. Am. Chem. Soc. 2011, 133, 1726; (b) X. Han, F. Zhong, Y. Wang, Y. Lu, Angew. Chem. Int. Ed. 2012, 51, 767; (c) F. Zhong, X. Han, Y. Wang, Y. Lu, Chem. Sci. 2012, 3, 1231; (d) F. Zhong, X. Han, Y. Wang, Y. Lu, Angew. Chem. Int. Ed. 2011, 50, 7837; (e) F. Zhong, J. Luo, G.-Y. Chen, X. Dou, Y. Lu, J. Am. Chem. Soc. 2012, 134, 10222; (f) F. Zhong, X. Dou, X. Han, W. Yao, Q, Zhu, Y. Meng, Y. Lu, Angew. Chem. Int. Ed. 2013, 52, 943; (g) T. Wang, W. Yao, F. Zhong, G. H. Pang, Y. Lu, Angew. Chem. Int. Ed. 2014, 53, 2964.

[2] X. Dou, Y. Lu, Org. Biomol. Chem., 2013, 11, 5217.

[3] X. Gu, Y. Zhang, Z.-J. Xu, C.-M. Che, Chem. Commun., 2014, 50, 7870.

8. NMR Spectra of the Products

0.90

97

1.97

54

1.00

00

9.16

32

Inte

gral

8.13

18

7.40

06

7.38

42

7.38

17

7.37

03

7.35

27

7.26

06

5.70

36

5.60

15

1.63

53

(ppm)

0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0

*** Current Data Parameters ***

NAME : wtl-1114

EXPNO : 3

PROCNO : 1

*** Acquisition Parameters ***

LOCNUC : 2H

NS : 37

NUCLEUS : off

O1 : 3088.51 Hz

PULPROG : zg30

SFO1 : 500.1330885 MHz

SOLVENT : CDCl3

SW : 20.6557 ppm

TD : 32768

TE : 297.9 K

*** Processing Parameters ***

LB : 0.30 Hz

SF : 500.1300134 MHz

*** 1D NMR Plot Parameters ***

NUCLEUS : off

1H AMX500

HDL-75

168.

3434

168.

1977

148.

3979

141.

8757

141.

8392

128.

1463

128.

1244

127.

0750

125.

8143

125.

7852

120.

5893

120.

4581

119.

2338

85.6

172

85.2

309

83.7

152

77.2

585

77.0

035

76.7

557

27.9

886

(ppm)

102030405060708090100110120130140150160170180190


NAME : wtl-1114

EXPNO : 2

PROCNO : 1


LOCNUC : 2H

NS : 415

NUCLEUS : off

O1 : 13204.57 Hz

PULPROG : zgpg30

SFO1 : 125.7709936 MHz

SOLVENT : CDCl3

SW : 238.7675 ppm

TD : 65536

TE : 298.5 K


LB : 1.00 Hz

SF : 125.7577906 MHz


NUCLEUS : off

13C AMX500

HDL-75

-187

.103

5-1

87.2

860

(ppm)

-215-210-205-200-195-190-185-180-175-170-165-160-155


NAME : nov14-~1

EXPNO : 4

PROCNO : 1


LOCNUC : 2H

NS : 43

NUCLEUS : off

O1 : -28240.22 Hz

PULPROG : zg

SFO1 : 282.3761148 MHz

SOLVENT : DMSO

SW : 239.2822 ppm

TD : 131072

TE : 296.3 K


LB : 0.30 Hz

SF : 282.4043550 MHz


NUCLEUS : off

F19(no decoupled)

HDL-75

-187

.103

5

-187

.286

0

(ppm)

-188.0-187.0-186.0

0.99

21

0.96

50

1.02

89

1.00

00

9.15

85

Inte

gral

7.96

407.

9464

7.38

667.

3236

7.30

597.

2606

5.76

785.

6670

1.63

27

(ppm)

0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5


NAME : wtl-1108

EXPNO : 1

PROCNO : 1


LOCNUC : 2H

NS : 34

NUCLEUS : off

O1 : 3088.51 Hz

PULPROG : zg30

SFO1 : 500.1330885 MHz

SOLVENT : CDCl3

SW : 20.6557 ppm

TD : 32768

TE : 300.0 K


LB : 0.30 Hz

SF : 500.1300134 MHz


NUCLEUS : off

1H AMX500

hdl-70(5-CF3 sub)

0.99

21

0.96

50

1.02

89

Inte

gral

7.96

407.

9464

7.38

66

7.32

367.

3059

7.26

06(ppm)

7.37.47.57.67.77.87.98.08.1

168.

2419

168.

1034

148.

4494

146.

0956

139.

3693

139.

3329

124.

6051

123.

2205

123.

0820

121.

4278

119.

3728

119.

1104

116.

9898

85.5

448

85.1

877

83.6

647

77.2

518

76.9

967

76.7

489

27.9

818

(ppm)

102030405060708090100110120130140150160170180190


NAME : wtl-1108

EXPNO : 2

PROCNO : 1


LOCNUC : 2H

NS : 743

NUCLEUS : off

O1 : 13204.57 Hz

PULPROG : zgpg30

SFO1 : 125.7709936 MHz

SOLVENT : CDCl3

SW : 238.7675 ppm

TD : 65536

TE : 300.2 K


LB : 1.00 Hz

SF : 125.7577906 MHz


NUCLEUS : off

13C AMX500

hdl-70(5-CF3 sub)

-58.

2780

-188

.443

3-1

88.6

222

(ppm)

-200-180-160-140-120-100-80-60-40-200


NAME : nov08-~1

EXPNO : 8

PROCNO : 1


LOCNUC : 2H

NS : 14

NUCLEUS : off

O1 : -28240.22 Hz

PULPROG : zg

SFO1 : 282.3761148 MHz

SOLVENT : CDCl3

SW : 239.2822 ppm

TD : 131072

TE : 298.5 K


LB : 0.30 Hz

SF : 282.4043550 MHz


NUCLEUS : off

F19(no decoupled)

hdl-70(5-CF3 sub)

-188

.443

3-1

88.6

222

(ppm)

-190-188-186

-193

.678

5-1

93.8

574

(ppm)

-210-200-190-180-170-160-150-140-130-120-110


NAME : nov20-~1

EXPNO : 1

PROCNO : 1


LOCNUC : 2H

NS : 17

NUCLEUS : off

O1 : -28240.22 Hz

PULPROG : zg

SFO1 : 282.3761148 MHz

SOLVENT : CDCl3

SW : 239.2822 ppm

TD : 131072

TE : 299.1 K


LB : 0.30 Hz

SF : 282.4043550 MHz


NUCLEUS : off

F19(no decoupled)

wtl-1051

-193

.678

5

-193

.857

4

(ppm)

-194.4-194.0-193.6-193.2-192.8-192.4

1.04

90

2.06

54

5.02

76

1.06

60

1.02

58

1.00

00

2.14

43

1.14

50

1.06

84

9.18

70

Inte

gral

7.42

20

7.40

69

7.38

04

7.37

54

7.36

65

7.36

27

7.35

14

7.34

76

7.33

75

7.33

38

7.33

00

7.32

37

7.31

48

7.31

11

7.26

06

7.23

92

7.22

41

7.20

89

6.89

50

6.88

24

6.87

86

6.86

48

6.85

09

6.84

71

6.83

45

5.99

61

5.96

46

5.16

53

3.15

19

3.14

81

3.13

80

3.13

55

3.12

29

3.11

28

3.10

90

3.10

65

3.09

77

3.09

39

3.08

38

3.08

13

2.96

53

2.94

89

2.94

64

2.93

51

2.92

62

2.92

37

2.91

99

2.91

74

2.90

73

2.89

72

2.87

83

1.63

27

(ppm)

0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5


NAME : wtl-1101

EXPNO : 3

PROCNO : 1


LOCNUC : 2H

NS : 30

NUCLEUS : off

O1 : 3088.51 Hz

PULPROG : zg30

SFO1 : 500.1330885 MHz

SOLVENT : CDCl3

SW : 20.6557 ppm

TD : 32768

TE : 297.8 K


LB : 0.30 Hz

SF : 500.1300134 MHz


NUCLEUS : off

1H AMX500

wtl-1038

1.04

90

2.06

54

5.02

76

1.06

60

Inte

gral

7.91

75

7.90

11

7.46

61

7.44

97

7.43

71

7.43

46

7.43

08

7.42

20

7.40

69

7.38

04

7.37

54

7.36

65

7.36

27

7.35

14

7.34

76

7.33

75

7.33

38

7.33

00

7.32

37

7.31

48

7.31

11

7.26

06

7.23

92

7.22

41

7.20

89

(ppm)

7.37.47.57.67.77.87.98.0

-148

.981

9-1

49.0

257

-149

.047

6-1

49.0

951

(ppm)

-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-100


NAME : nov08-~1

EXPNO : 4

PROCNO : 1


LOCNUC : 2H

NS : 6

NUCLEUS : off

O1 : -28240.22 Hz

PULPROG : zg

SFO1 : 282.3761148 MHz

SOLVENT : CDCl3

SW : 239.2822 ppm

TD : 131072

TE : 298.5 K


LB : 0.30 Hz

SF : 282.4043550 MHz


NUCLEUS : off

F19(no decoupled)

wtl-1038

-148

.981

9-1

49.0

257

-149

.047

6-1

49.0

951

(ppm)

-149.6-149.2-148.8-148.4

NBoc

O

FCOOBn

7b

Cl

-149

.562

4-1

49.6

135

-149

.671

9

(ppm)

-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-100


NAME : nov08-~1

EXPNO : 2

PROCNO : 1


LOCNUC : 2H

NS : 35

NUCLEUS : off

O1 : -28240.22 Hz

PULPROG : zg

SFO1 : 282.3761148 MHz

SOLVENT : CDCl3

SW : 239.2822 ppm

TD : 131072

TE : 298.6 K


LB : 0.30 Hz

SF : 282.4043550 MHz


NUCLEUS : off

F19(no decoupled)

wtl-1040

-149

.562

4-1

49.6

135

-149

.671

9

(ppm)

-150.8-150.4-150.0-149.6-149.2

NBoc

O

FCOOBn

7b

Cl

-148

.751

9-1

48.7

957

-148

.821

3-1

48.8

651

(ppm)

-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-100


NAME : nov08-~1

EXPNO : 3

PROCNO : 1


LOCNUC : 2H

NS : 37

NUCLEUS : off

O1 : -28240.22 Hz

PULPROG : zg

SFO1 : 282.3761148 MHz

SOLVENT : CDCl3

SW : 239.2822 ppm

TD : 131072

TE : 298.5 K


LB : 0.30 Hz

SF : 282.4043550 MHz


NUCLEUS : off

F19(no decoupled)

wtl-1039

-148

.751

9-1

48.7

957

-148

.821

3-1

48.8

651

(ppm)

-149.6-149.2-148.8-148.4

0.8

61

3

7.0

35

4

1.0

01

7

1.0

00

0

2.2

34

8

1.1

07

4

1.0

92

9

8.9

78

0

Inte

gra

l

8.1

58

37

.38

54

7.3

67

87

.35

77

7.3

50

17

.34

51

7.3

36

37

.32

87

7.2

60

66

.85

47

6.8

40

86

.83

83

6.8

24

46

.81

05

6.8

06

86

.79

29

5.9

89

85

.95

83

5.1

69

1

3.1

31

73

.12

92

3.1

17

93

.11

53

3.1

04

03

.09

01

3.0

77

53

.07

50

3.0

64

93

.06

24

2.9

32

52

.91

49

2.9

03

52

.89

22

2.8

87

12

.87

58

2.8

63

22

.84

68

1.6

27

7

︵ppm ︶

0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5


NAME : wtl-1115

EXPNO : 1

PROCNO : 1


DS : 0

INSTRUM : spect

LOCNUC : 2H

NS : 30

NUCLEUS : off

O1 : 3088.51 Hz

PULPROG : zg30

SFO1 : 500.1330885 MHz

SOLVENT : CDCl3

SW : 20.6557 ppm

TD : 32768

TE : 297.8 K


LB : 0.30 Hz

OFFSET : 16.477 ppm

SI : 16384


NUCLEUS : off

1H AMX500

wtl-1054

16

9.4

95

01

69

.32

74

16

5.1

73

6

14

8.2

88

81

41

.08

88

14

1.0

52

41

38

.26

86

13

8.2

10

31

35

.68

89

12

8.5

98

31

28

.49

63

12

8.3

28

71

28

.20

48

12

8.0

15

31

27

.84

77

12

7.0

67

91

26

.06

23

12

2.7

53

81

22

.60

08

11

9.3

94

3

91

.33

07

89

.80

76

85

.79

95

77

.25

87

77

.00

37

76

.74

86

66

.44

43

38

.18

39

37

.95

07

27

.96

70

︵ppm ︶

102030405060708090100110120130140150160170180190


NAME : wtl-1115

EXPNO : 2

PROCNO : 1


DS : 0

INSTRUM : spect

LOCNUC : 2H

NS : 3577

NUCLEUS : off

O1 : 13204.57 Hz

PULPROG : zgpg30

SFO1 : 125.7709936 MHz

SOLVENT : CDCl3

SW : 238.7675 ppm

TD : 65536

TE : 298.1 K


LB : 1.00 Hz

OFFSET : 224.383 ppm

SI : 32768


NUCLEUS : off

13C AMX500

wtl-1054

-149

.171

7-1

49.2

155

-149

.241

1-1

49.2

849

(ppm)

-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-100


NAME : nov17-~1

EXPNO : 1

PROCNO : 1


LOCNUC : 2H

NS : 93

NUCLEUS : off

O1 : -28240.22 Hz

PULPROG : zg

SFO1 : 282.3761148 MHz

SOLVENT : CDCl3

SW : 239.2822 ppm

TD : 131072

TE : 299.2 K


LB : 0.30 Hz

SF : 282.4043550 MHz


NUCLEUS : off

F19(no decoupled)

wtl-1054

-149

.171

7-1

49.2

155

-149

.241

1-1

49.2

849

(ppm)

-149.6-149.2-148.8-148.4

1.01

72

6.13

01

1.11

00

1.00

29

1.00

00

2.19

98

1.07

54

1.03

71

9.40

70

Inte

gral

7.98

93

7.97

17

7.36

52

7.36

15

7.35

01

7.34

51

7.34

00

7.33

12

7.32

36

7.30

60

7.27

83

7.26

06

6.86

73

6.85

46

6.85

09

6.83

70

6.82

31

6.81

93

6.80

55

5.99

36

5.96

20

5.17

28

3.14

56

3.14

18

3.13

17

3.12

92

3.11

66

3.10

27

3.09

01

3.08

76

3.07

75

2.95

02

2.93

25

2.92

12

2.90

73

2.90

48

2.89

22

2.88

08

2.86

19

1.62

64

(ppm)

0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5


NAME : wtl-1110

EXPNO : 1

PROCNO : 1


LOCNUC : 2H

NS : 34

NUCLEUS : off

O1 : 3088.51 Hz

PULPROG : zg30

SFO1 : 500.1330885 MHz

SOLVENT : CDCl3

SW : 20.6557 ppm

TD : 32768

TE : 299.9 K


LB : 0.30 Hz

SF : 500.1300134 MHz


NUCLEUS : off

1H AMX500

wtl-1045

NBoc

O

FCOOBn

7e

F3C

16

9.4

36

21

69

.26

86

16

5.0

63

8

14

8.3

39

31

46

.07

29

13

8.5

59

61

38

.51

59

13

7.8

74

61

37

.82

36

13

5.6

88

41

28

.56

86

12

8.2

99

01

28

.16

05

12

7.3

22

51

25

.45

69

12

5.3

03

91

24

.67

72

12

1.3

97

91

19

.35

01

11

8.1

62

31

17

.17

85

91

.30

10

89

.76

34

85

.73

35

77

.25

82

77

.00

32

76

.74

81

66

.45

11

38

.32

18

38

.08

86

27

.97

37

︵ppm ︶

102030405060708090100110120130140150160170180190


NAME : wtl-1110

EXPNO : 2

PROCNO : 1


DS : 0

INSTRUM : spect

LOCNUC : 2H

NS : 12547

NUCLEUS : off

O1 : 13204.57 Hz

PULPROG : zgpg30

SFO1 : 125.7709936 MHz

SOLVENT : CDCl3

SW : 238.7675 ppm

TD : 65536

TE : 300.2 K


LB : 1.00 Hz

OFFSET : 224.383 ppm

SI : 32768


NUCLEUS : off

13C AMX500

wtl-1045

13

8.5

59

61

38

.51

59

13

7.8

74

61

37

.82

36

13

5.6

88

4

12

8.5

68

61

28

.29

90

12

8.1

60

51

27

.32

25

12

5.4

56

91

25

.30

39

12

4.6

77

2

︵ppm ︶

128132136

NBoc

O

FCOOBn

7e

F3C

-58.

2816

-150

.727

0-1

50.7

744

-150

.800

0-1

50.8

438

(ppm)

-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-10010


NAME : nov10-~1

EXPNO : 1

PROCNO : 1


LOCNUC : 2H

NS : 40

NUCLEUS : off

O1 : -28240.22 Hz

PULPROG : zg

SFO1 : 282.3761148 MHz

SOLVENT : CDCl3

SW : 239.2822 ppm

TD : 131072

TE : 298.8 K


LB : 0.30 Hz

SF : 282.4043550 MHz


NUCLEUS : off

F19(no decoupled)

wtl-1045

-150

.727

0-1

50.7

744

-150

.800

0-1

50.8

438

(ppm)

-151.6-151.2-150.8-150.4

NBoc

O

FCOOBn

7e

F3C

170.

2600

170.

0924

165.

3119

148.

5873

138.

9170

138.

8587

137.

7583

137.

7146

135.

7907

134.

9745

134.

9527

132.

3511

132.

3292

128.

5616

128.

2556

128.

1317

126.

6305

125.

2678

123.

8613

123.

7155

115.

5537

91.8

624

90.3

467

85.0

196

77.2

585

77.0

035

76.7

484

66.3

129

38.3

586

38.1

181

28.0

178

20.9

782

(ppm)

102030405060708090100110120130140150160170180190


NAME : wtl-1101

EXPNO : 2

PROCNO : 1


LOCNUC : 2H

NS : 6825

NUCLEUS : off

O1 : 13204.57 Hz

PULPROG : zgpg30

SFO1 : 125.7709936 MHz

SOLVENT : CDCl3

SW : 238.7675 ppm

TD : 65536

TE : 298.1 K


LB : 1.00 Hz

SF : 125.7577916 MHz


NUCLEUS : off

13C AMX500

wtl-1037

-148

.405

1-1

48.4

525

-148

.470

8-1

48.5

182

(ppm)

-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-100


NAME : nov08-~1

EXPNO : 6

PROCNO : 1


LOCNUC : 2H

NS : 30

NUCLEUS : off

O1 : -28240.22 Hz

PULPROG : zg

SFO1 : 282.3761148 MHz

SOLVENT : CDCl3

SW : 239.2822 ppm

TD : 131072

TE : 298.5 K


LB : 0.30 Hz

SF : 282.4043550 MHz


NUCLEUS : off

F19(no decoupled)

wtl-1037

-148

.405

1-1

48.4

525

-148

.470

8

-148

.518

2

(ppm)

-149.2-148.8-148.4-148.0

-149

.485

7-1

49.5

368

-149

.555

1-1

49.6

062

(ppm)

-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-100


NAME : nov08-~1

EXPNO : 7

PROCNO : 1


LOCNUC : 2H

NS : 75

NUCLEUS : off

O1 : -28240.22 Hz

PULPROG : zg

SFO1 : 282.3761148 MHz

SOLVENT : CDCl3

SW : 239.2822 ppm

TD : 131072

TE : 298.5 K


LB : 0.30 Hz

SF : 282.4043550 MHz


NUCLEUS : off

F19(no decoupled)

wtl-1036

-149

.485

7-1

49.5

368

-149

.555

1-1

49.6

062

(ppm)

-150.0-149.6-149.2-148.8

5.04

32

1.99

11

0.98

27

1.00

00

1.97

75

1.01

97

1.02

91

3.02

24

3.04

51

9.06

13

Inte

gral

7.37

297.

3602

7.35

657.

3464

7.34

267.

3338

7.33

137.

3249

7.31

747.

2606

7.05

016.

8484

6.83

586.

8320

6.81

816.

8043

6.80

056.

7879

5.97

475.

9432

5.16

03

3.08

133.

0776

3.06

753.

0649

3.05

233.

0385

3.02

593.

0233

3.01

333.

0095

2.96

532.

9628

2.94

642.

9363

2.92

882.

9200

2.91

742.

9124

2.90

992.

9010

2.89

852.

8834

2.31

232.

1925

1.59

87

(ppm)

0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5


NAME : wtl-1105

EXPNO : 1

PROCNO : 1


LOCNUC : 2H

NS : 38

NUCLEUS : off

O1 : 3088.51 Hz

PULPROG : zg30

SFO1 : 500.1330885 MHz

SOLVENT : CDCl3

SW : 20.6557 ppm

TD : 32768

TE : 300.1 K


LB : 0.30 Hz

SF : 500.1300134 MHz


NUCLEUS : off

1H AMX500

wtl-1041

171.

2510

171.

0834

165.

2899

148.

4051

139.

0481

138.

9898

136.

1404

136.

0967

135.

8562

135.

2805

135.

2513

134.

9599

134.

9380

128.

5397

128.

2117

128.

1097

126.

4992

125.

2604

125.

1146

124.

5462

122.

7899

92.6

056

91.0

826

85.2

818

77.2

584

77.0

034

76.7

483

66.2

618

38.5

698

38.3

293

27.7

553

20.8

542

19.4

842

(ppm)

102030405060708090100110120130140150160170180190


NAME : wtl-1108

EXPNO : 3

PROCNO : 1


LOCNUC : 2H

NS : 3932

NUCLEUS : off

O1 : 13204.57 Hz

PULPROG : zgpg30

SFO1 : 125.7709936 MHz

SOLVENT : CDCl3

SW : 238.7675 ppm

TD : 65536

TE : 300.1 K


LB : 1.00 Hz

SF : 125.7577906 MHz


NUCLEUS : off

13C AMX500

wtl-1041

-149

.252

1-1

49.2

959

-149

.354

3

(ppm)

-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-100


NAME : nov08-~1

EXPNO : 1

PROCNO : 1


LOCNUC : 2H

NS : 68

NUCLEUS : off

O1 : -28240.22 Hz

PULPROG : zg

SFO1 : 282.3761148 MHz

SOLVENT : CDCl3

SW : 239.2822 ppm

TD : 131072

TE : 298.6 K


LB : 0.30 Hz

SF : 282.4043550 MHz


NUCLEUS : off

F19(no decoupled)

wtl-1041

-149

.252

1-1

49.2

959

-149

.354

3

(ppm)

-149.6-149.2-148.8-148.4

0.97

27

5.06

07

0.96

84

0.96

10

0.98

59

0.92

58

1.00

00

2.03

04

1.05

87

1.06

62

Inte

gral

7.50

277.

4888

7.38

427.

3691

7.36

277.

3577

7.34

767.

3388

7.32

877.

3224

7.26

067.

1497

7.13

467.

1194

6.98

586.

9757

6.96

696.

9543

6.94

426.

9354

6.75

386.

7374

5.96

965.

9659

5.96

215.

9381

5.93

435.

9306

5.78

055.

6784

5.15

77

4.55

134.

5475

4.54

124.

5375

4.51

484.

5110

4.50

594.

5022

4.41

644.

4126

4.40

634.

4026

4.37

994.

3761

4.36

984.

3660

(ppm)

0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5


NAME : wtl-1125

EXPNO : 3

PROCNO : 1


LOCNUC : 2H

NS : 26

NUCLEUS : off

O1 : 3088.51 Hz

PULPROG : zg30

SFO1 : 500.1330885 MHz

SOLVENT : CDCl3

SW : 20.6557 ppm

TD : 32768

TE : 299.3 K


LB : 0.30 Hz

SF : 500.1300134 MHz


NUCLEUS : off

1H AMX500

wtl-1056

0.97

27

5.06

07

0.96

84

0.96

10

7.50

277.

4888

7.38

427.

3691

7.36

277.

3577

7.34

767.

3388

7.32

877.

3224

7.26

06

7.14

977.

1346

7.11

94

6.98

586.

9757

6.96

696.

9543

6.94

426.

9354

(ppm)

7.007.107.207.307.407.50

170.

8498

170.

7040

165.

1729

143.

2962

143.

2598

140.

5343

135.

5279

131.

5927

131.

5708

128.

6049

128.

4008

128.

3790

126.

3968

123.

6859

123.

6640

123.

1029

122.

7458

122.

6146

109.

2788

85.9

665

84.4

580

77.2

508

77.0

030

76.7

479

66.6

258

40.6

171

(ppm)

102030405060708090100110120130140150160170180190


NAME : wtl-1125

EXPNO : 4

PROCNO : 1


LOCNUC : 2H

NS : 12100

NUCLEUS : off

O1 : 13204.57 Hz

PULPROG : zgpg30

SFO1 : 125.7709936 MHz

SOLVENT : CDCl3

SW : 238.7675 ppm

TD : 65536

TE : 299.2 K


LB : 1.00 Hz

SF : 125.7577907 MHz


NUCLEUS : off

13C AMX500

wtl-1056

131.

5927

131.

5708

128.

6049

128.

4008

128.

3790

126.

3968

123.

6859

123.

6640

123.

1029

122.

7458

122.

6146

(ppm)

123124125126127128129130131132

-192

.466

5-1

92.6

454

(ppm)

-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-10


NAME : nov24wtl

EXPNO : 1

PROCNO : 1


LOCNUC : 2H

NS : 56

NUCLEUS : off

O1 : -28240.22 Hz

PULPROG : zg

SFO1 : 282.3761148 MHz

SOLVENT : CDCl3

SW : 239.2822 ppm

TD : 131072

TE : 299.3 K


LB : 0.30 Hz

SF : 282.4043550 MHz


NUCLEUS : off

F19(no decoupled)

wtl-1056

-192

.466

5-1

92.6

454

(ppm)

-194.0-193.0-192.0-191.0-190.0

0.96

25

2.00

33

1.00

89

1.00

00

1.10

34

0.96

23

1.10

60

1.10

26

9.33

63

Inte

gral

7.89

357.

8771

7.46

997.

4547

7.44

847.

4447

7.44

217.

4295

7.41

697.

4131

7.26

067.

2379

7.22

287.

2076

5.60

535.

6015

5.58

895.

5863

5.58

265.

5700

5.56

365.

5510

5.54

735.

5347

5.16

155.

1489

5.12

87

3.00

562.

9930

2.98

042.

9779

2.97

292.

9678

2.96

532.

9552

2.94

262.

8821

2.86

572.

8543

2.84

802.

8380

2.83

162.

8203

2.80

391.

6365

(ppm)

0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5


NAME : wtl-1125

EXPNO : 1

PROCNO : 1


LOCNUC : 2H

NS : 30

NUCLEUS : off

O1 : 3088.51 Hz

PULPROG : zg30

SFO1 : 500.1330885 MHz

SOLVENT : CDCl3

SW : 20.6557 ppm

TD : 32768

TE : 298.8 K


LB : 0.30 Hz

SF : 500.1300134 MHz


NUCLEUS : off

1H AMX500

wtl-1057-2

0.96

25

2.00

33

1.00

89

Inte

gral

7.89

357.

8771

7.46

997.

4547

7.44

847.

4447

7.44

217.

4295

7.41

697.

4131

7.26

067.

2379

7.22

287.

2076

(ppm)

7.37.47.57.67.77.87.9

170.

7848

170.

6172

148.

7113

140.

2143

140.

1778

131.

3965

131.

3747

128.

4379

128.

3723

124.

8379

124.

6776

124.

5246

121.

5003

115.

4663

92.5

038

90.9

954

84.9

250

77.2

514

76.9

963

76.7

413

40.0

639

39.8

380

28.0

397

(ppm)

102030405060708090100110120130140150160170180190


NAME : wtl-1125

EXPNO : 2

PROCNO : 1


LOCNUC : 2H

NS : 766

NUCLEUS : off

O1 : 13204.57 Hz

PULPROG : zgpg30

SFO1 : 125.7709936 MHz

SOLVENT : CDCl3

SW : 238.7675 ppm

TD : 65536

TE : 299.5 K


LB : 1.00 Hz

SF : 125.7577906 MHz


NUCLEUS : off

13C AMX500

wtl-1057-2

131.

3965

131.

3747

128.

4379

128.

3723

124.

8379

124.

6776

124.

5246

(ppm)

124125126127128129130131132

-149

.394

4-1

49.4

346

-149

.452

9-1

49.4

930

(ppm)

-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-10


NAME : nov24wtl

EXPNO : 2

PROCNO : 1


LOCNUC : 2H

NS : 204

NUCLEUS : off

O1 : -28240.22 Hz

PULPROG : zg

SFO1 : 282.3761148 MHz

SOLVENT : CDCl3

SW : 239.2822 ppm

TD : 131072

TE : 299.3 K


LB : 0.30 Hz

SF : 282.4043550 MHz


NUCLEUS : off

F19(no decoupled)

wtl-1057-2

-149

.394

4-1

49.4

346

-149

.452

9

-149

.493

0

(ppm)

-149.8-149.6-149.4-149.2-149.0

0.91

00

1.84

82

0.94

77

2.04

69

9.00

00

1.11

75

1.14

38

3.03

72

Inte

gral

7.90

237.

8847

7.44

347.

4396

7.42

837.

4245

7.41

327.

4094

7.26

067.

2442

7.22

917.

2140

2.23

162.

2215

2.20

892.

2051

2.19

882.

1950

2.18

242.

1761

2.17

232.

1660

2.15

212.

1421

2.12

572.

1156

2.10

172.

0916

2.07

522.

0664

1.64

151.

3276

1.31

751.

3024

1.29

111.

2772

1.26

211.

2545

1.20

911.

2041

1.19

401.

1877

1.18

011.

1663

1.15

491.

1410

1.12

970.

9179

0.90

280.

8876

(ppm)

0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5


NAME : wtl-1127

EXPNO : 2

PROCNO : 1


LOCNUC : 2H

NS : 29

NUCLEUS : off

O1 : 3088.51 Hz

PULPROG : zg30

SFO1 : 500.1330885 MHz

SOLVENT : CDCl3

SW : 20.6557 ppm

TD : 32768

TE : 298.8 K


LB : 0.30 Hz

SF : 500.1300134 MHz


NUCLEUS : off

1H AMX500

wtl-1057-3(a)

171.

4116

171.

2367

148.

8062

140.

2872

140.

2435

131.

2655

131.

2436

125.

2825

125.

1295

124.

9473

124.

9254

124.

4226

115.

4956

93.5

679

92.0

885

84.8

959

77.2

515

76.9

964

76.7

413

37.8

049

37.5

863

28.0

544

16.1

468

16.0

958

13.9

461

(ppm)

102030405060708090100110120130140150160170180190


NAME : wtl-1129

EXPNO : 1

PROCNO : 1


LOCNUC : 2H

NS : 3660

NUCLEUS : off

O1 : 13204.57 Hz

PULPROG : zgpg30

SFO1 : 125.7709936 MHz

SOLVENT : CDCl3

SW : 238.7675 ppm

TD : 65536

TE : 299.6 K


LB : 1.00 Hz

SF : 125.7577906 MHz


NUCLEUS : off

13C AMX500

wtl-1057-3(a)

125.

2825

125.

1295

124.

9473

124.

9254

124.

4226

(ppm)

124.0124.4124.8125.2125.6

-148

.244

4-1

48.2

956

-148

.343

0

(ppm)

-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-100


NAME : nov27wtl

EXPNO : 1

PROCNO : 1


LOCNUC : 2H

NS : 93

NUCLEUS : off

O1 : -28240.22 Hz

PULPROG : zg

SFO1 : 282.3761148 MHz

SOLVENT : CDCl3

SW : 239.2822 ppm

TD : 131072

TE : 298.9 K


LB : 0.30 Hz

SF : 282.4043550 MHz


NUCLEUS : off

F19(no decoupled)

wtl-1057-3(a)

-148

.244

4-1

48.2

956

-148

.343

0

(ppm)

-148.8-148.4-148.0-147.6-147.2

enantioselective synthesis of 3-fluoro-3-allyl-oxindoles via phos … · 2015. 5. 14. · 3 bn(6c)...

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