Supporting Information (Part 1)
Efficient 1,4-addition of -substituted
fluoro(phenylsulfonyl)methane derivatives to ,-unsaturated
compounds
G. K. Surya Prakash,* Xiaoming Zhao, Sujith Chacko, Fang Wang, Habiba Vaghoo and George A.
Olah*
Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern
California, Los Angeles, California 90089-1661
gprakash@usc.edu, olah@usc.edu
Supporting Information
S2-S13
Spectra
S14-S34
- S1 -
Experimental Section
Unless otherwise mentioned, all other reagents were purchased from commercial sources. Diethyl
ether and THF were all distilled under nitrogen over sodium/benzophenone prior to use. Toluene was
distilled over sodium. Column chromatography was carried out using silica gel (60-200 mesh).
1
H,
13
C and
19
F NMR spectra were recorded on Varian Mercury 400 NMR spectrometers. 1H NMR
chemical shifts were determined relative to internal (CH3)4Si (TMS) at δ 0.0 ppm or to the signal of a
residual protonated solvent: CDCl3 δ 7.26 ppm. 13C NMR chemical shifts were determined relative to
internal TMS at δ 0.0 ppm or to the
13C
signal of solvent: CDCl3 δ 77.16 ppm.
19F
NMR chemical
shifts were determined relative to internal CFCl3 at δ 0.0 ppm.
A general procedure for the oxidation of sulfides
Aqueous hydrogen peroxide (13.5 mL, 160 mmol, 30% wt) was added into a solution of the sulfide
(40 mmol) in CH3CO2H (60 mL) at 0 C and the reaction mixture was stirred about 2 h. The reaction
mixture was allowed to warm to room temperature and stirred overnight. The mixture was poured into
ice water (200 mL) and extracted with dichloromethane (200 mL). The organic phase was washed
with ice water (200 mL × 3), dried over MgSO4, and evaporated. The residue was purified by column
chromatography to afford the title product (2a–2e). The characterization data of (2a–2e) [1-6], 3a [7],
3c [8] and 3d [9] are consistent with those reported earlier.
(Nitromethylsulfonyl)benzene (2a):
O
O
S
NO2
White solid, 90% yield. 1H NMR (CDCl3):  5.60 (s, 2H), 7.64–7.68 (m, 2H), 7.78–7.82 (m, 1H),
7.96–7.99 (m, 2H).
2-(Phenylsulfonyl)acetonitrile (2b):
O
O
S
CN
- S2 -
Colorless oil, 76% yield. 1H NMR (CDCl3):  4.07 (s, 2H), 7.65–7.70 (m, 2H), 7.77–7.82 (m, 1H),
8.04–8.06 (m, 2H).
Ethyl 2-(phenylsulfonyl)acetate (2c):
O
O
S
CO2Et
Colorless oil, in 83% yield. 1H NMR (CDCl3):  1.29 (t, J = 7.2 Hz, 3H), 4.26–4.42 (m, 2H), 7.59–
7.64 (m, 2H), 7.73–7.78 (m, 1H), 7.93–7.95 (m, 2H).
1-(Phenylsulfonyl)propan-2-one (2d):
O
O
S
COMe
Colorless oil, in 70% yield. 1H NMR (CDCl3):  2.42 (s, 3H), 4.16 (s, 2H), 7.57–7.61 (m, 2H), 7.68–
7.72 (m, 1H), 7.88–7.91 (m, 2H).
(Allylsulfonyl)benzene (2e):
O
O
S
Ph
Colorless oil, in 91% yield. 1H NMR (CDCl3):  3.80–3.82 (m, 2H), 5.12–5.13 (m, 1H), 5.16–5.17 (m,
1H), 5.74–5.84 (m, 1H), 7.53–7.58 (m, 2H), 7.63–7.86 (m, 1H), 7.87–7.89 (m, 2H).
Improved procedure for the monofluorination with Selectfluor: To a slurry of NaH (6.75 mmol) in
THF (15 mL) was added a solution of 1-substituted (phenylsulfonyl)methane (6.75 mmol) in THF (10
mL) at 0 C under argon. After stirring for 2 h, a solution of Selectfluor (6.75 mmol) in anhydrous
DMF (15 mL) was added dropwise to the above-mentioned mixture at 0 C and the reaction mixture
was stirred overnight, and monitored by TLC. After completion of the reaction, CH2Cl2 (20 mL) was
added and the mixture was washed with water, brine, then the organic phase was dried with MgSO4
and filtered. The filtrate was evaporated, and the residue was purified by column chromatography to
give the title product in good yield.
- S3 -
[Fluoro(nitro)methylsulfonyl]benzene (3a):
O
O
S
NO2
F
White solid isolated in 62% yield. 1H NMR (CDCl3):  6.44 (d, J = 48.4 Hz, 1H), 7.66−7.70 (m, 2H),
7.83−7.87 (m, 1H), 7.94−7.96 (m, 2H).
C NMR (CDCl3):  111.81 (d, J = 283.0 Hz), 130.06,
13
130.72, 131.43, 136.84. 19F NMR (CDCl3):  −142.16 (d, J = 48.4 Hz, 1F).
2-Fluoro-2-(phenylsulfonyl)acetonitrile (3b):
O
O
S
CN
F
Colorless oil isolated in 45% yield. 1H NMR (CDCl3):  5.69 (d, J = 46.8 Hz, 1H), 7.68–7.73 (m, 2H),
7.84–7.88 (m, 1H), 8.04–8.07 (m, 2H). 13C NMR (CDCl3):  88.11 (d, J = 232.3 Hz), 109.87 (d, J =
29.5 Hz), 130.00, 130.69, 132.25, 136.59. 19F NMR (CDCl3):  −179.23 (d, J = 47.8 Hz, 1F). HRMS
Calcd for C8H6FNO2S: 199.0103; Found: 199.0107.
Ethyl 2-fluoro-2-(phenylsulfonyl)acetate (3c):
F
O
OEt
S
O O
Colorless oil isolated in 56% yield. 1H NMR (CDCl3):  1.29 (t, J = 7.2 Hz, 3H), 4.29 (q, 2H), 5.57 (d,
J = 48.0 Hz, 1H), 7.59–7.64 (m, 2H), 7.73–7.78 (m, 1H), 7.93–7.96 (m, 2H).
13C
NMR (CDCl3): 
14.03, 63.64, 97.39 (d, J = 232.5 Hz), 129.54, 129.93, 134.65, 135.46, 161.11 (d, J = 22.9 Hz).
NMR (CDCl3):  −180.91 (d, J = 48.0 Hz, 1F).
1-Fluoro-1-(phenylsulfonyl)propan-2-one (3d):
F
O
S
O O
- S4 -
19
F
White solid isolated in 61% yield. 1H NMR (CDCl3):  2.37 (d, J = 3.6 Hz, 3H), 5.46 (d, J = 49.2 Hz,
1H), 7.61–7.65 (m, 2H), 7.75–7.77 (m, 1H), 7.92–7.95 (m, 2H). 13C NMR (CDCl3):  27.65, 101.51
(d, J = 874.8 Hz), 129.68, 129.74, 134.95, 135.51, 195.71 (d, J = 81.7 Hz).
19F
NMR (CDCl3): 
−113.56 (tq, J = 49.2 Hz, 3.6 Hz, 1F).
General procedure:
To a solution of fluorine-substituted active methylene derivative (0.2 mmol, 1 equivalent) and methyl
vinyl ketone (0.6 mmol, 3 equivalents) in THF (0.5 mL) was added trimethylphosphine (0.04 mmol,
1.0 M in THF) dropwise by syringe at room temperature under argon, and the reaction was monitored
by TLC. After completion of the reaction, the solvents were removed under vacuum. The crude
products were purified by column chromatography (hexane/ ethyl acetate = 3/1) to afford the products
in good to excellent yield.
5-Fluoro-5-nitro-5-(phenylsulfonyl)pentan-2-one (5a):
F
NO2
O
S
O
O
White solid isolated in 93% yield. 1H NMR (CDCl3):  2.18 (s, 3H), 2.50–2.56 (m, 1H), 2.70–2.78 (m,
1H), 2.88–2.92 (m, 1H), 2.98–3.09 (m, 1H), 7.62–7.66 (m, 2H), 7.79–7.83 (m, 1H), 7.91–7.94 (m,
2H).
13C
NMR (CDCl3):  25.56 (d, J = 17.9 Hz), 27.19, 30.01, 35.53 (d, J = 2.2 Hz), 123.63 (d,
J=282.4), 125.04, 129.91, 131.09, 131.33, 136.55, 203.79.
19F
NMR (CDCl3):  −125.90, −125.96
(dd, J1 = 28.6 Hz, 10.5 Hz, 1F). HRMS: (FAB) calcd for C11H13FNO5S 290.0499 (M+1) found: m/z
290.0500.
2-Fluoro-5-oxo-2-(phenylsulfonyl)hexanenitrile (5b):
F
CN
O
S
O
O
- S5 -
White solid isolated in 90% yield. 1H NMR (CDCl3):  2.23 (s, 3H), 2.66–2.75 (m, 1H), 2.85–2.92 (m,
1H), 7.65–7.69 (m, 2H), 7.81–7.85 (m, 1H), 8.02–8.04 (m, 2H).
13C
NMR (CDCl3):  25.84 (d, J =
21.4 Hz), 30.00, 36.82 (d, J = 2.4 Hz), 99.20 (d, J = 228.8 Hz), 112.24 (d, J = 33.1 Hz), 129.75,
131.14, 132.04, 136.32, 204.03. 19F NMR (CDCl3):  −148.50 (dd, J= 27.1 Hz, 16.9 Hz, 1F). HRMS:
(FAB) calcd for C12H13FNO3S 270.0600 (M+1) found: m/z 270.0612.
Ethyl 2-fluoro-5-oxo-2-(phenylsulfonyl)hexanoate (5c):
F
CO2Et
O
S
O
O
White solid isolated in 75% yield. 1H NMR (CDCl3):  1.20 (t, J = 7.2 Hz, 3H), 2.14 (s, 3H), 2.49–
2.56 (m, 2H), 2.67–2.78 (m, 2H), 4.15–4.23 (m, 2H), 7.56–7.60 (m, 2H), 7.70–7.74 (m, 1H), 7.89–
7.92 (m, 2H). 13C NMR (CDCl3):  13.93, 25.28 (d, J = 19.9 Hz), 29.92, 36.48 (d, J = 3.2 Hz), 63.58,
106.26 (d, J = 233.3 Hz), 129.30, 130.45, 134.13, 135.24, 163.63 (d, J = 24.8 Hz), 205.27. 19F NMR
(CDCl3):  −158.34 (m, 1F). HRMS: (FAB) calcd for C14H18FNO5S 317.0859 (M+1) found: m/z
317.0861.
5-Fluoro-5,5-bis(phenylsulfonyl)pentan-2-one (5d):
O
S
O
O
S
F
O
CH3
O
White solid isolated in 91% yield. 1H NMR (CDCl3):  2.17 (s, 3H), 2.56–2.64 (m, 2H), 3.05–3.09 (m,
2H), 7.55–7.59 (m, 4H), 7.72–7.76 (m, 2H), 7.91–7.93 (m, 4H).
13C
NMR (CDCl3):  24.81 (d, J =
18.9 Hz), 29.95, 36.51 (d, J = 6.2 Hz), 115.07 (d, J = 264.4 Hz), 129.20, 130.99, 134.89, 135.52. 19F
NMR (CDCl3):  −140.70 (t, J = 15.4 Hz, 1F). HRMS: (FAB) calcd for C17H18FO5S2 385.0580 (M+1)
found: m/z 385.0565.
- S6 -
Ethyl 4-fluoro-4-nitro-4-(phenylsulfonyl)butanoate (5e):
F
NO2
O
OEt
S
O
O
White solid isolated in 64% yield. 1H NMR (CDCl3):  1.26 (t, J = 7.2 Hz, 3H), 2.31–2.39 (m, 1H),
2.50–2.58 (m, 1H), 2.87–2.95 (m, 1H), 3.04–3.20 (m, 1H), 4.11 (q, J = 7.2 Hz, 2H), 7.58–7.62 (m,
2H), 7.76–7.80 (m, 1H), 7.88–7.90 (m, 2H). 13C NMR (CDCl3):  14.37, 26.70 (d, J = 18.2 Hz), 27.04
(d, J = 3.8 Hz), 61.73, 123.43 (d, J = 282.8 Hz), 130.04, 131.22, 131.27, 136.73, 170.35.
19
F NMR
(CDCl3):  −126.70 (dd, J= 30.1 Hz, 9.8 Hz, 1F). HRMS: (FAB) calcd for C12H15FNO6S 320.0604
(M+1) found: m/z 320.0612.
Ethyl 4-cyano-4-fluoro-4-(phenylsulfonyl)butanoate (5f)
F
CN
O
S
O
OEt
O
White solid isolated in 60% yield. 1H NMR (CDCl3):  1.30 (t, J = 7.2 Hz, 3H), 2.70–2.83 (m, 4H),
4.17–4.22 (m, J = 7.2 Hz, 2H), 7.66–7.70 (m, 2H), 7.81–7.86 (m, 1H), 8.03–8.06 (m, 2H). 13C NMR
(CDCl3):  14.32, 27.59 (d, J = 18.9 Hz), 28.33 (d, J = 3.0 Hz), 61.59, 99.04 (d, J = 228.8 Hz), 112.15
(d, J = 33.2 Hz), 129.86, 131.28, 132.08, 136.44, 170.49.
19F
NMR (CDCl3):  −149.63 (m, 1F).
HRMS: (FAB) calcd for C13H15FNO4S 300.0706 (M+1) found: m/z 300.0719.
Diethyl 2-fluoro-2-(phenylsulfonyl)pentanedioate (5g):
F
CO2Et
O
OEt
S
O
O
White solid isolated in 71% yield. 1H NMR (CDCl3):  1.18–1.25 (m, 6H), 2.32–2.38 (m, 1H), 2.55–
2.59 (m, 2H), 2.76–2.84 (m, 1H), 4.06–4.21 (m, 4H), 7.54–7.58 (m, 2H), 7.68–7.72 (m, 1H), 7.87–
7.90 (m, 2H). 13C NMR (CDCl3):  14.15, 14.41, 26.63 (d, J = 20.2 Hz), 28.05 (d, J = 3.4 Hz), 61.31,
- S7 -
63.82, 106.38 (d, J = 234.5 Hz), 129.51, 130.67, 134.23, 135.47, 163.61 (d, J = 25.5 Hz), 171.40. 19F
NMR (CDCl3):  −159.13 (dd, J= 31.2 Hz, 10.5 Hz, 1F). HRMS: (FAB) calcd for C15H20FNO6S
347.0965 (M+1) found: m/z 347.0962.
Ethyl 4-fluoro-4,4-bis(phenylsulfonyl)butanoate (5h):
O
S
O
O
S
F
O
OEt
O
White solid isolated in 88% yield. 1H NMR (CDCl3):  1.20 (t, J = 7.2 Hz, 3H), 2.62–2.71 (m, 2H),
2.78–2.83 (m, 2H), 4.04–4.09 (m, 2H), 7.51–7.56 (m, 2H), 7.68–7.72 (m, 1H), 7.88–7.90 (m, 2H). 13C
NMR (CDCl3):  14.22, 26.01 (d, J = 19.4 Hz), 27.69 (d, J = 7.7 Hz), 61.06, 114.75 (d, J = 266.1 Hz),
129.21, 130.96, 134.85, 135.52, 171.43. 19F NMR (CDCl3):  −142.91 (t, J = 15.8 Hz, 1F). HRMS:
(FAB) calcd for C18H20FO6S2 415.0685 (M+1) found: m/z 415.0673.
General procedure:
To a solution of fluorine-substituted active methylene derivative (0.16 mmol, 1 equivalent) and ,unsaturated compound (0.16 mmol, 1 equivalent) in DMF (2 mL) was added potassium carbonate
(0.36 mmol, 0.050 g) at room temperature and the reaction was monitored by
19F
NMR. Aqueous
work up followed by extraction with dichloromethane (3 x 15 mL) afforded the crude product. The
pure product was obtained by column chromatography.
4,4-Bis(benzenesulfonyl)-4-fluoro-2-methyl-butyric acid methyl ester (6a)
O
(PhSO2)2FC
O
Colorless oil isolated in 70% yield. 1H NMR (CDCl3):  1.18 (d, J = 6.8 Hz, 3H), 2.44–2.58 (m, 1H),
2.50–2.58 (m, 1H), 2.92 (dd, J = 29.4 Hz, 0.5 Hz, 1H), 2.96–3.11 (m, 2H), 3.51 (s, 3H), 7.55–7.61 (m,
4H), 7.71–7.77 (m, 2H), 7.87–7.99 (m, 4H). 13C NMR (CDCl3):  18.99, 32.84 (d, J = 17.5 Hz), 34.74
- S8 -
(d, J = 5.8 Hz), 51.95, 114.80 (d, J = 268.6 Hz), 128.96, 129.01, 130.93, 130.95, 134.41, 134.77,
135.28, 135.32, 175.07
19
F NMR (CDCl3):  −146.50 (dd, J = 22.8 Hz, 10.5 Hz, 1F) HRMS: (FAB)
calcd for C18H19FO6S2 415.0685 (M+1) found: m/z 415.0668.
4,4-Bis(benzenesulfonyl)-4-fluoro-2-methyl-butyric acid tert-butyl ester (6c)
(PhSO2)2FC
O
O
White solid isolated in 70% yield. 1H NMR (CDCl3):  1.13 (d, J = 7.1Hz, 3H), 1.34 (s, 9H), 2.43 (ddd,
J =23.5 Hz, 15.8 Hz, 3.9 Hz, 1H), 2.80 –2.90 (m, 1H), 2.91–3.02 (m, 1H), 7.54–7.62 (m, 4H), 7.70–7.77
(m, 2H), 7.88–8.00 (m, 4H). 13C NMR (CDCl3):  19.03, 27.75 (d, J = 11.9 Hz), 32.81 (d, J = 17.3
Hz), 35.76 (d, J = 5.7 Hz), 80.52, 115.11 (d, J = 268.4 Hz), 128.96, 129.01, 130.96, 134.53, 134.95,
135.23, 135.26, 173.93.
19F
NMR (CDCl3):  −146.17 (dd, J = 10.7 Hz, 23.6 Hz, 1F) HRMS: (FAB)
calcd for C21H25FO6S2 457.1155 (M+1) found: m/z 457.1147.
3-[Bis(benzenesulfonyl)-fluoro-methyl]-cyclohexanone (6d)
O
H
CF(SO2Ph)2
White solid isolated in 90% yield. 1H NMR (CDCl3):  1.40–1.56 (m, 1H), 2.15–2.25 (m, 1H), 2.30–
2.47 (m, 3H), 2.52–2.80 (m, 3H), 3.03–3.13 (m, 1H), 7.48–7.57 (m, 4H), 7.68–7.75 (m, 2H), 7.77–7.83 (m,
2H), 7.85–7.91 (m, 2H)
13C
NMR (CDCl3):  25.10, 25.15, 41.07, 41.36 (d, J = 6.9 Hz), 42.67 (d, J =
17.2 Hz), 114.41 (d, J = 266.4 Hz), 114.45, 128.83, 129.09, 130.58, 130.59, 130.76, 130.78, 134.87,
135.20, 135.34, 135.77, 207.82.
19F
NMR (CDCl3):  −136.36 (s, 1F) HRMS: (FAB) calcd for
C19H19FO5S2 411.0736 (M+1) found: m/z 411.0740.
6,6-Bis(benzenesulfonyl)-6-fluoro-hexan-3-one (6e)
O
(PhSO2)2FC
White solid isolated in 79% yield. 1H NMR (CDCl3): .1.04 (d, J = 7.4 Hz, 3H), 2.46 (q, J = 7.3 Hz,
- S9 -
2H), 2.58–2.68 (m, 2H), 3.00–3.08 (m, 2H), 7.55–7.62 (m, 4H), 7.70–7.77 (m, 2H), 7.90–7.95 (m, 4H)
13
C
NMR (CDCl3):  24.75 (d, J = 18.4 Hz), 35.00, 35.05, 35.82, 115.03 (d, J = 264.5 Hz), 129.06,
130.83, 130.85, 134.79, 135.37, 207.99.
F NMR (CDCl3):  −140.74 (t, J = 15.9 Hz, 1F) HRMS:
19
(FAB) calcd for C18H19FO5S2 399.0736 (M+1) found: m/z 399.0742.
3,3-Bis(benzenesulfonyl)-3-fluoro-1-(methylsulfonyl)propane (6f)
(PhSO 2)2FC
O2
S
White solid isolated in 60% yield. 1H NMR (CDCl3): .2.77–2.87 (m, 2H), 2.99 (s, 3H), 3.60 –3.67 (m,
2H), 7.57–7.63 (m, 4H), 7.74–7.80 (m, 2H), 7.91–7.96 (m, 4H)
13C
NMR (CDCl3):  24.01(d, J = 20.7
Hz), 40.99, 48.12 (d, J = 6.9 Hz), 113.11 (d, J = 266.1Hz), 129.29, 130.94, 134.01, 135.82
19F
NMR
(CDCl3):  −140.35 (t, J = 14.0 Hz, 1F) HRMS: (FAB) calcd for C16H17FO6S3 421.0249 (M+1) found:
m/z 421.0262.
4,4-Bis(benzenesulfonyl)-4-fluoro-butyronitrile (6g)
(PhSO2)2FC
CN
White solid. 1H NMR (CDCl3):  2.70–2.79 (m, 2H), 2.91–2.97 (m, 2H), 7.56–7.63 (m, 4H), 7.80–7.74
(m, 2H), 7.88–7.93 (m, 4H). 13C NMR (CDCl3):  12.07 (d, J = 9.2 Hz), 26.94 (d, J = 18.4 Hz), 113.00
(d, J = 267.6 Hz), 117.561, 129.34, 130.83, 134.10, 135.82. 19F NMR (CDCl3):  −145.04 (t, J = 15.5
Hz, 1F) HRMS: (FAB) calcd for C16H14FNO4S2 368.0426 (M+1) found: m/z 368.0445.
2-[2,2-Bis(benzenesulfonyl)-2-fluoroethyl]-pentanedinitrile (6h)
(PhSO2)2FC
CN
CH2CH2CN
White solid. 1H NMR (CDCl3):  1.90–2.20 (m, 2H), 2.43–2.68 (m, 2H), 2.76–2.88 (m, 2H), 3.32–3.42
(m, 1H), 7.55–7.64 (m, 4H), 7.74–7.82 (m, 2H), 7.84–7.88 (m, 2H), 7.93–7.97 (m, 2H).
13C
NMR
(CDCl3):  15.09, 25.95 (d, J = 5.4 Hz), 28.81, 32.13 (d, J = 17.6 Hz), 112.95 (d, J = 269.9 Hz),
117.37, 118.56, 129.32, 129.51, 130.80, 131.01, 133.35, 133.95, 135.95. 19F NMR (CDCl3):  −146.55
- S10 -
(dd, J = 19.5 Hz, 12.9 Hz, 1F) HRMS: (FAB) calcd for C19H17FN2O4S2 421.0692 (M+1) found: m/z
421.0688.
4,4-Bis(benzenesulfonyl)-4-fluoro-but-2-enoic acid methyl ester (6j)
cis
O
(PhSO2)2FC
O
H NMR (CDCl3):  3.75 (s, 3H), 5.97 (d, J = 15.7 Hz, 1H), 7.27 (dd, J = 23.1 Hz, 15.7 Hz, 1H), 7.55–
1
7.61 (m, 4H), 7.72–7.78 (m, 2H), 7.91–7.96 (m, 4H). 13C NMR (CDCl3):  52.43, 112.86 (d, J = 269.1
Hz), 129.12, 129.77 (d, J = 9.2 Hz), 130.59 (d, J = 14.6 Hz), 130.89, 134.40, 135.79.
19F
NMR
(CDCl3):  −150.93 (d, J = 23.1 Hz, 1F) HRMS: (FAB) calcd for C17H15FO6S2 399.0372 (M+1) found:
m/z 399.0379.
trans
(PhSO2)2FC
O
O
1H
NMR (CDCl3):  3.42 (s, 3H), 6.18 (dd, J = 12.9 Hz, 1.3 Hz, 1H), 6.44 (dd, J = 28.5 Hz, 12.9 Hz, 1H),
7.56–7.62 (m, 4H), 7.73–7.78 (m, 2H), 7.93–7.98 (m, 4H).
13C
NMR (CDCl3):  51.96, 113.53 (d, J =
273.0 Hz), 121.26 (d, J = 13.80 Hz), 128.98, 130.78 (d, J = 3.07 Hz), 131.06, 134.48, 135.54, 164.13.
19F
NMR (CDCl3):  −150.60 (d, J = 28.5 Hz, 1F) HRMS: (FAB) calcd for C17H15FO6S2 399.0372
(M+1) found: m/z 399.0379.
4,4-Bis(benzenesulfonyl)-4-fluoro-but-2-enoic acid ethyl ester (6k)
cis
O
(PhSO2)2FC
O
White solid. 1H NMR (CDCl3):  1.28 (t, J = 7.1 Hz, 3H), 4.19 (q, J = 7.1 Hz, 2H), 5.96 (dd, J = 15.7
Hz, 0.4 Hz, 1H), 7.25 (dd, J = 23.1 Hz, 15.7 Hz, 1H), 7.55–7.62 (m, 4H), 7.72–7.78 (m, 2H), 7.91–
7.96 (m, 4H). 13C NMR (CDCl3) :  14.00, 61.44, 112.80 (d, J = 269.1 Hz), 129.06, 130.09 (d, J = 9.1
- S11 -
Hz), 130.21 (d, J = 3.2 Hz), 130.79, 134.31, 135.75, 163.23. 19F NMR (CDCl3):  −150.90 (d, J = 23.1
Hz, 1F) HRMS: (FAB) calcd for C18H17FO6S2 413.0529 (M+1) found: m/z 413.0543.
trans
(PhSO2 )2FC
O
O
White solid. 1H NMR (CDCl3):  1.07 (dt, J = 7.1 Hz, 0.4 Hz, 3H), 3.91 (q, J = 7.1Hz, 2H), 6.17 (dd, J =
12.9 Hz, 1.3 Hz, 1H), 6.41 (dd, J = 28.7 Hz, 13.0 Hz, 1H), 7.56–7.62 (m, 4H), 7.73–7.78 (m, 2H), 7.94–
7.98 (m, 4H).
13
C NMR (CDCl3):  13.85, 61.08, 113.63 (d, J = 274.0 Hz), 120.68 (d, J = 13.8 Hz),
128.97, 130.98, 130.99, 131.26 (d, J = 2.9 Hz), 134.55, 135.50, 163.69. 19F NMR (CDCl3):  −150.32
(d, J = 28.7 Hz, 1F) HRMS: (FAB) calcd for C18H17FO6S2 413.0529 (M+1) found: m/z 413.0543.
4-(Benzenesulfonyl)-4-fluoro-4-nitro-but-2-enoic acid ethyl ester (6l)
NO2 H
PhSO2FC
H
O
O
White solid. 1H NMR (CDCl3):  1.23 (t, J = 7.1 Hz), 4.16 (q , J = 7.2 Hz), 6.50 (dd, J = 12.4, 2.4 Hz,
1H), 6.79 (dd, J = 18.7, 12.3 Hz, 1H), 7.63–7.69 (m, 2H), 7.81–7.87 (m, 1H), 7.92–7.97 (m, 2H). 13C
NMR (CDCl3):  13.78, 61.94, 123.83 (d, J = 15.3 Hz), 129.68, 131.17, 131.50 (d, J = 288.3 Hz),
136.56, 163.12.
19F
NMR (CDCl3):  −119.05 (d, J = 18.3 Hz, 1F)
HRMS: (FAB) calcd for
C12H12FNO6S 318.0447 (M+1) found: m/z 318.0445.
References
1. Wade, P. A.; Hinney, H. R.; Amin, N. V.; Vail, P. D.; Morrow, S. D.; Hardinger, S. A.; Saft, M.
S. J. Org. Chem. 1981, 46, 765–770. doi:10.1021/jo00317a023
2. Truce, W. E.; Klingler, T. C.; Paar, J. E.; Feuer, H.; Wu, D. K. J. Org. Chem. 1969, 34, 3104–
3107. doi:10.1021/jo01262a068
3. Walker, D. J. Org. Chem. 1966, 31, 835–837. doi:10.1021/jo01341a045
4. Doyle, K. J.; Moody, C. J. Tetrahedron 1994, 50, 3761–3772. doi:10.1016/S0040-
- S12 -
4020(01)90396-5
5. Ohta,
H.;
Kato,
Y.;
Tsuchihashi,
G.
J.
Org.
Chem.
1987,
52,
2735–2739.
Lett.
2007,
48,
4407–4411.
doi:10.1021/jo00389a018
6. Sheldrake,
H.
M.;
Wallace,
T.
W.
Tetrahedron
doi:10.1016/j.tetlet.2007.04.099
7. Prakash, G. K. S.; Chacko, S.; Alconcel, S.; Stewart, T.; Mathew, T.; Olah, G. A. Angew.
Chem., Int. Ed. 2007, 46, 4933–4936. doi:10.1002/anie.200700834
8. Takeuchi, Y.; Asahina, M.; Hori, K.; Koizumi, T. J. Chem. Soc., Perkin Trans. 1 1988, 1149–
1153. doi:10.1039/P19880001149
9. Takeuchi, Y.; Ogura, H.; Kanada, A.; Koizumi, T. J. Org. Chem. 1992, 57, 2196–2199.
doi:10.1021/jo00033a058
- S13 -
0.916
1.563
7.986
7.983
7.969
7.965
7.962
7.797
7.678
7.659
7.657
7.639
7.259
5.604
OO
S
Ph
NO2
8.00 7.95 7.90 7.85 7.80 7.75 7.70 7.65
PPM
2.13
2.03
1.90
1.00
6
4
2
0
PPM
0
PPM
1.563
8
4.064
10
8.059
8.056
8.038
8.035
7.795
7.693
7.673
7.672
7.260
12
Ph
O O
S
CN
1.97
1.79
1.00
1.97
1.79
8.2
8.1
8.0
7.9
7.8
7.7
2.19
PPM
7.6
1.00
12
10
8
6
- S14 -
4
2
7.914
7.909
7.907
7.906
7.904
7.903
7.893
7.889
7.888
7.884
7.718
7.715
7.711
7.702
7.696
7.692
7.681
7.677
7.675
7.612
7.609
7.608
7.606
7.604
7.591
7.587
7.584
7.573
7.571
7.570
7.568
7.260
4.159
2.418
2.417
Ph
12
12
10
10
O O
S
8
O
OEt
8
8.0
4.33
3.13
1.85 1.87
1.10
4.20 4.18 4.16 4.14 4.12 4.10
PPM
6
4
1.90
1.77
7.9
7.8
7.7
6
- S15 7.6
2
4
0
OO
S
Ph
2
PPM
O
3.00
2.15
0.94
PPM
7.5
0
PPM
1.616
1.202
1.184
1.166
7.962
7.961
7.959
7.947
7.942
7.941
7.938
7.692
7.691
7.604
7.603
7.588
7.587
7.586
7.584
7.583
4.164
4.146
4.128
4.113
7.961
7.959
7.941
7.938
7.873
7.870
7.866
7.851
7.847
7.835
7.832
7.829
7.696
7.691
7.677
7.675
7.661
7.658
7.656
7.260
6.504
6.383
OO
S
Ph
1.891.99
12
12
10
1.05
10
8
2.09
5.8
0.99
0.91
8
6
8.1
6
- S16 -
8.0
7.9
4
7.8
5.7
7.7
5.6
4
Ph
2
5.5
5.4
2
O O
S
5.3
0
0
5.2
PPM
1.00
0.00
1.02
PPM
NO 2
F
1.93 2.04
1.11
PPM
PPM
7.889
7.884
7.882
7.881
7.879
7.877
7.868
7.862
7.859
7.672
7.669
7.665
7.656
7.650
7.645
7.634
7.632
7.628
7.577
7.574
7.572
7.568
7.563
7.556
7.552
7.549
7.547
7.538
7.534
7.532
7.260
5.842
5.823
5.817
5.805
5.798
5.781
5.774
5.762
5.756
5.737
5.344
5.342
5.339
5.337
5.319
5.317
5.314
5.312
5.169
5.166
5.163
5.159
5.126
5.123
5.120
5.117
3.821
3.818
3.815
3.802
3.800
3.797
1.621
77.464
77.145
76.821
131.425
130.715
130.055
136.841
OO
NO2
S
Ph
F
135
134
133
132
131
200
130
PPM
150
100
50
0
PPM
-142.117
-142.248
136
-0.010
137
OO
NO2
S
Ph
F
-141.9
0
-50
-142.0
-142.1
-142.2
-142.3
-142.4 PPM
-100
- S17 -
-150
-200
PPM
200
136
135
134
8
133
132
131
150
6
100
- S18 77.441
77.398
77.318
77.168
77.124
76.846
76.802
76.762
76.539
1.00
89.259
86.958
10
110.017
109.724
12
132.252
130.689
129.999
136.594
Ph
O O
S
CN
F
1.95
2.13
0.89
4
2
50
0
PPM
OO
CN
S
Ph
F
130
PPM
0
PPM
8.072
8.067
8.066
8.062
8.061
8.054
8.051
8.046
8.042
7.867
7.865
7.862
7.859
7.857
7.848
7.845
7.842
7.838
7.732
7.730
7.728
7.727
7.723
7.718
7.711
7.707
7.705
7.704
7.701
7.699
7.692
7.689
7.687
7.684
7.683
7.264
7.260
7.253
5.751
5.747
5.741
5.634
5.629
5.623
2.177
2.173
2.167
1.558
1.555
1.549
7.955
7.954
7.952
7.951
7.939
7.935
7.933
7.931
7.930
7.755
7.737
7.636
7.635
7.633
7.631
7.617
7.616
7.614
7.597
7.596
7.260
5.630
5.510
4.322
4.305
4.303
4.286
4.284
1.607
1.304
1.286
1.268
-0.010
Ph
-179.10
0
-50
12
10
8
-179.15
4.330
-179.20
4.320
-179.25
4.310
6
- S19 -
-179.30
4.300
-179.35
-100
4.290
4
4.280
O O
S
-150
2
CN
F
PPM
-200
PPM
OO O
S
OEt
Ph
F
4.270
8.0 7.9 7.8 7.7 7.6
0
PPM
-179.162
-179.289
0.006
-0.001
14.029
63.639
77.462
77.147
76.822
98.542
96.231
135.461
134.647
129.929
129.909
129.535
161.227
160.999
OO O
S
OEt
Ph
F
135
161.6 161.4 161.2 161.0 160.8
150
133
132
100
131
130
50
0
PPM
-180.848
-180.976
200
134
OO O
S
OEt
Ph
F
-180.6-180.7-180.8-180.9-181.0-181.1-181.2
0
-50
-100
- S20 -
-150
-200
PPM
7.950
7.949
7.947
7.946
7.944
7.930
7.928
7.926
7.924
7.772
7.769
7.767
7.752
7.748
7.654
7.651
7.650
7.648
7.646
7.633
7.631
7.629
7.627
7.616
7.613
7.611
7.609
7.259
5.525
5.402
2.371
2.362
1.585
Ph
200
8.0
12
150
7.9
7.8
7.7
10
100
Ph
8
OO
S
F
6
- S21 -
4
O O
S
2
O
F
135.7135.6135.5135.4135.3135.2135.1135.0
129.85129.80129.75129.70129.65129.60
196.0 195.9 195.8 195.7 195.6 195.5 195.4
50
0
0
PPM
O
2.4002.3902.3802.3702.3602.350
3.17
1.99
1.80
7.6
0.98
1.05
PPM
27.648
77.464
77.140
76.829
102.659
100.335
135.514
134.947
129.742
129.675
195.818
195.601
0
-50
1.61
12
0.82
10
8
3.127
3.114
3.102
3.089
3.074
3.063
3.056
3.049
3.042
3.030
3.016
3.002
2.991
2.977
2.943
2.931
2.918
2.905
2.892
2.879
2.866
2.852
2.840
2.782
2.770
2.756
2.744
2.736
2.724
2.711
2.699
2.574
2.560
2.549
2.535
2.529
2.515
2.504
2.489
2.230
2.180
1.561
0.066
7.938
7.936
7.934
7.917
7.915
7.912
7.834
7.832
7.828
7.817
7.812
7.808
7.797
7.794
7.791
7.664
7.661
7.656
7.641
7.640
7.625
7.621
7.260
OO O
S
Ph
F
-179.95 -180.00 -180.05 -180.10 -180.15 -180.20
-100
3.2
-150
3.1
0. 99
3.0
2.9
1. 00
6
- S22 -
2.8
1. 00
2.7
2.6
1.61
0.82
1.83
4
-200
PhSO2
2
PPM
O
F NO
2
1. 09
2.5
8.2 8.1 8.0 7.9 7.8 7.7 7.6
1.83
0.99
1.00
1.00
1.09 3.01
0
PPM
-180.013
-180.022
-180.035
-180.042
-180.143
-180.152
-180.164
-180.171
0
-125.907
-125.935
-125.983
-126.012
-0.003
-0.010
PhSO2
200
PhSO2
-50
O
F NO
2
35.7 35.6 35.5 35.4 35.3
25.7
150
100
F NO
-125.7
-100
- S23 -
-150
-125.8
-125.9
-126.0
-200
25.6
25.5
50
25.4
0
25.3
136 135 134 133 132 131 130
PPM
O
2
-126.1
PPM
83.315
77.044
76.884
76.740
76.611
76.523
76.441
76.307
76.211
76.119
75.862
75.765
75.693
75.641
75.411
66.916
64.165
35.542
35.520
33.860
30.011
27.193
25.647
25.599
25.421
25.373
23.062
-4.002
79.960
79.659
78.859
78.608
78.524
77.513
77.405
77.203
136.555
136.501
131.329
131.107
131.094
131.046
129.906
125.039
122.232
157.712
186.437
193.831
203.789
200
1.73
2.01
7.8
7.7
10
8
PhSO2
150
6
112.4
112.3
100
- S24 112.2
37.2
37.0
36.832
36.808
30.003
25.951
25.738
7.9
77.454
77.139
76.814
8.0
100.333
98.058
12
8.1
112.409
112.079
8.2
136.316
132.038
131.136
129.754
204.027
PhSO 2
O
F CN
3.14
1.91
2.00
0.93
7.6
3.00 2.95 2.90 2.85 2.80 2.75 2.70 2.65
4
2
36.8
50
0
26.4
26.2
PPM
O
F CN
112.1
36.6
26.0
25.8
0
25.6
PPM
8.038
8.035
8.018
7.847
7.844
7.840
7.829
7.825
7.821
7.809
7.806
7.803
7.691
7.686
7.672
7.656
7.651
7.259
2.915
2.911
2.891
2.871
2.854
2.752
2.738
2.734
2.730
2.720
2.716
2.710
2.693
2.674
2.655
2.282
2.231
7.922
7.918
7.915
7.913
7.910
7.901
7.896
7.894
7.891
7.742
7.739
7.725
7.722
7.721
7.718
7.716
7.705
7.701
7.699
7.602
7.599
7.596
7.594
7.580
7.578
7.575
7.564
7.559
7.558
7.259
4.225
4.215
4.207
4.202
4.198
4.188
4.184
4.180
4.166
4.162
4.158
4.149
2.780
2.776
2.775
2.752
2.750
2.725
2.711
2.692
2.689
2.686
2.681
2.674
2.564
2.558
2.547
2.542
2.537
2.527
2.521
2.513
2.511
2.504
2.491
2.137
1.221
1.203
1.184
-148.35-148.40-148.45-148.50-148.55-148.60
PhSO2
0
8.0
7.9
12
7.8
7.7
10
O
F CN
-50
-100
8
-150
2.9
4.26 4.24 4.22 4.201.93
4.18 4.16 4.14 4.12
1.77
6
- S25 2.8
2.7
2.6
2.00
4
-200
PhSO2
3.00
2
PPM
O
F COOEt
7.6
2.5
2.13
3.06
2.17
0.91
0
PPM
-148.441
-148.486
-148.513
-148.552
-0.001
-158.281
-158.288
-158.301
-158.314
-158.323
-158.348
-158.363
-158.371
-158.380
-158.389
-158.403
PhSO2
200
0
-50
O
F COOEt
36.60 36.55 36.50 36.45 36.40
163.9 163.8 163.7 163.6 163.5
25.45 25.40 25.35 25.30 25.25 25.20 25.15
150
100
PhSO2
-158.20
-158.25
-158.30
-158.35
-100
- S26 50
-150
0
-200
PPM
O
F COOEt
-158.40
PPM
36.497
36.465
29.924
25.381
25.183
13.929
77.464
77.145
76.820
63.584
107.421
105.102
135.237
134.129
130.448
129.295
163.752
163.505
205.270
3.80
7.9
7.8
12
200
7.7
7.6
10
8
PhSO2
150
2.9
2.8
6
100
- S27 -
2.7
2.00
36.542
36.480
29.945
24.899
24.711
3.0
77.462
77.146
76.822
135.519
134.887
130.991
129.594
129.202
116.385
113.757
205.264
PhSO2
O
F SO Ph
2
2.6
4.00
2.06
3.01
2.09
4
2
50
0
25.0
24.9
24.8
PPM
F SO Ph
2
O
36.70 36.65 36.60 36.55 36.50 36.45 36.40
24.7
0
PPM
7.928
7.926
7.907
7.755
7.753
7.740
7.738
7.736
7.734
7.732
7.720
7.717
7.715
7.593
7.589
7.574
7.572
7.558
7.553
7.260
7.258
3.086
3.068
3.048
2.641
2.624
2.621
2.619
2.601
2.586
2.585
2.581
2.563
2.168
0
1. 76
8.0
7.9
12
7.8
7.7
10
8
4.135
4.116
4.099
4.081
3.197
3.182
3.172
3.158
3.143
3.133
3.123
3.118
3.109
3.098
3.084
3.069
3.059
3.044
2.951
2.938
2.928
2.915
2.913
2.904
2.899
2.890
2.876
2.576
2.562
2.550
2.537
2.533
2.520
2.508
2.495
2.389
2.374
2.364
2.350
2.332
2.322
2.307
1.273
1.256
1.223
1.206
1.188
7.896
7.876
7.799
7.796
7.793
7.778
7.761
7.758
7.755
7.623
7.618
7.604
7.587
7.583
7.227
PhSO2
O
F SO Ph
2
-140.62
-140.64
-140.66
-140.68
-140.70
-140.72
-140.74
-50
-100
PhSO2
F NO
2
-150
0. 97
3.4
6
- S28 3.2
3.0
2.8
0. 92
4
2.6
-200
1. 02
1. 08
0.92
1.02
0.97
2
PPM
O
OEt
1. 04
3.31
1.95
2.4
1.91
1.76
1. 91
1.08
1.04
7.6
0
PPM
-140.660
-140.699
-140.742
-0.004
OEt
2
27.2
131.3
131.2
27.1
27.0
26.9
26.8
26.7
131.1
150
100
50
0
PPM
-126.645
-126.671
-126.725
-126.747
-0.003
200
27.061
27.023
26.791
26.610
14.366
O
F NO
131.4
61.731
77.665
77.343
77.020
136.725
131.271
131.221
130.036
124.832
122.021
170.350
PhSO2
PhSO2
O
F NO
2
OEt
-126.50-126.55-126.60-126.65-126.70-126.75
0
-50
-100
- S29 -
-150
-200
PPM
200
7.8
7.7
12
10
PhSO2
F CN
150
2.85
1.93
8
6
100
- S30 -
2.80
2.75
2.70
28.348
28.318
27.195
27.125
26.981
14.322
7.9
OEt
77.535
77.409
77.210
77.076
76.896
61.587
8.0
100.180
97.905
F CN
112.310
111.980
8.1
136.438
132.077
131.283
129.862
8.2
170.487
PhSO2
O
2.65
4.00
4
50
3.35
1.64
2.00
7.6
0.94
2
28.5
0
28.0
27.5
PPM
O
OEt
112.4 112.3 112.2 112.1 112.0 111.9 111.8
27.0
0
PPM
8.058
8.056
8.053
8.037
8.035
8.032
7.839
7.834
7.816
7.700
7.696
7.681
7.679
7.665
7.661
7.260
4.220
4.202
4.184
4.166
2.799
2.790
2.788
2.761
2.754
2.746
2.741
2.738
2.733
1.576
1.298
1.281
1.263
7.898
7.896
7.893
7.877
7.875
7.872
7.722
7.719
7.715
7.704
7.702
7.700
7.696
7.684
7.681
7.678
7.577
7.572
7.558
7.556
7.542
7.538
7.230
4.228
4.210
4.201
4.192
4.183
4.174
4.165
4.156
4.148
4.139
4.130
4.121
4.114
4.096
4.078
4.060
2.875
2.859
2.848
2.838
2.834
2.823
2.812
2.799
2.793
2.780
2.767
2.756
2.752
2.742
2.730
2.714
2.602
2.589
2.576
2.563
2.552
2.550
2.537
2.530
2.528
2.519
2.511
2.505
2.499
2.490
2.477
2.464
2.451
2.388
2.381
2.378
2.365
2.360
2.353
2.339
2.324
2.313
2.311
2.298
1.619
1.267
1.249
1.246
1.217
1.199
1.196
1.181
1.179
1.161
1.149
PhSO2
0
12
10
O
F CN
F COOEt
8
OEt
-149.45
-149.50
-149.55
-149.60
-149.65
-149.70
-149.75
-50
-100
PhSO2
4.20
-150
2.9
4.15
1.70
0.94
1.91
6
- S31 2.8
2.7
3.84
4
2.6
-200
2.5
2.4
1.26
0.922.00
1.02
2
PPM
O
OEt
2.3
7.95 7.90 7.85 7.80 7.75 7.70 7.65 7.60
4.10
1.24
1.22
0
1.20
1.18
1.16
6.02
PPM
1.14
-149.577
-149.587
-149.594
-149.624
-149.636
-149.659
-149.680
-149.689
-0.002
O
PhSO2
O
EtOOC
150
F
100
50
-159.073
-159.101
-159.156
-159.184
-0.002
ppm (f1)
PhSO2
F COOEt
O
OEt
-158.90
-158.95
-159.00
-159.05
-159.10
-159.15
-159.20
-159.25
0
-50
-100
- S32 -
-150
-200
PPM
7.8
200
7.7
12
10
8
PhSO2
F SO Ph
2
150
6
27.5
100
- S33 -
2.80
2.75
27.0
2.70
2.15
2.00
4
27.733
27.656
26.108
25.915
14.218
2.85
61.064
3.80
77.466
77.142
76.828
3. 80
135.523
134.849
130.967
130.951
129.214
116.070
113.425
7.9
171.438
171.421
PhSO2
O
F SO Ph
2
OEt
2. 09
2. 17
4.00
2.65
4. 00
2.09
3.34
2. 00
2.17
7.6
2
50
0
PPM
O
OEt
26.5
0
PPM
7.899
7.897
7.885
7.880
7.877
7.875
7.718
7.715
7.712
7.701
7.696
7.692
7.681
7.678
7.675
7.556
7.551
7.547
7.533
7.531
7.517
7.512
7.511
7.230
4.092
4.074
4.056
4.039
2.825
2.822
2.812
2.807
2.805
2.798
2.794
2.784
2.705
2.697
2.693
2.686
2.683
2.679
2.665
2.656
2.652
2.646
2.644
2.642
2.627
2.625
1.209
1.192
1.174
-142.867
-142.913
-142.951
PhSO2
O
F SO Ph
2
OEt
-142.80
0
-50
-100
- S34 -
-150
-142.85
-142.90
-142.95
-200
PPM