1515, 1455, 1365, 1296, 1258, 1181, 1056, 1024, 817 cm-1. 1H NMR
(CDCl3, 300 MHz): d 1.20 (s, 9H), 3.07 (dd, J = 6.8 Hz, J = 13.5 Hz,
2H), 3.53 (d, J = 7.9 Hz, 1H), 3.79 (s, 3H), 4.04–4.17 (m, 1H), 5.66
(d, J = 39.7 Hz, 1H), 6.83 (d, J = 8.8 Hz, 2H), 7.19–7.30 (m, 5H),
7.40 (d, J = 8.8 Hz, 2H) ppm. 19F NMR (CDCl3, 282.5 MHz): d
-120.2 (dd, J = 17.5 Hz, J = 39.2 Hz) ppm. 13C NMR (CDCl3,
75.4 MHz): d 22.5 (CH3), 39.8 (CH2), 55.4 (CH3), 56.5 (C), 59.8
(d, J = 27.9 Hz, CH), 108.3 (d, J = 7.1 Hz, CH), 113.9 (CH),
125.4 (d, J = 2.7 Hz, C), 127.0 (CH), 128.6 (CH), 129.7 (CH),
130.3 (d, J = 7.1 Hz, CH), 136.9 (C), 156.6 (d, J = 266.0 Hz, C),
159.0 (d, J = 2.7 Hz, C) ppm. MS (EI): m/z = 376.27 [M+H+].
Elemental analysis for C21H26FNO2S: C, 67.17; H, 6.98; N, 3.73;
S, 8.54. Found: C, 66.96; H, 6.85; N, 3.54; S, 8.47.
Dia 2: Yellow solid. Rf 0.28 (cyclohexane/EtOAc: 6/4). IR
(KBr): n 3197, 2960, 1690, 1610, 1515, 1455.4, 1365, 1296, 1258,
1181, 1056, 1024, 817 cm-1. 1H NMR (CDCl3, 300 MHz): d 1.19
(s, 9H), 3.14 (dd, J = 7.00 Hz, J = 13.4 Hz, 2H), 3.39 (d, J = 3.8 Hz,
1H), 3.81 (s, 3H), 4.16–4.29 (m, 1H), 5.57 (d, J = 39.4 Hz, 1H), 6.86
(d, J = 8.7 Hz, 2H), 7.22–7.30 (m, 5H), 7.40 (d, J = 8.6 Hz, 2H)
ppm. 19F NMR (CDCl3, 282.5 MHz): d -121.9 (dd, J = 19.6 Hz,
J = 39.2 Hz) ppm. 13C NMR (CDCl3, 75.4 MHz): d 22.6 (CH3),
39.8 (CH2), 55.4 (CH3), 56.2 (C), 58.3 (d, J = 27.4 Hz, CH), 109.2
(d, J = 7.1 Hz, CH), 114.0 (CH), 125.4 (d, J = 2.7 Hz, C), 127.2
(CH), 128.9 (CH), 129.7 (CH), 130.2 (d, J = 7.1 Hz, CH), 136.0
(C), 155.3 (d, J = 266.5 Hz, C), 159.0 (d, J = 2.7 Hz, C) ppm. MS
(EI): m/z = 376.27 [M+H]+. Elemental analysis for C21H26FNO2S:
C, 67.17; H, 6.98; N, 3.73; S, 8.54. Found: C, 66.94; H, 6.89; N,
3.56; S, 8.45.
19F NMR (CDCl3, 282.5 MHz): d -118.9 (dd, J = 18.6 Hz, J =
39.2 Hz) ppm. 13C NMR (CDCl3, 75.4 MHz): d 22.6 (CH3), 55.4
(CH3), 56.2 (C), 60.2 (d, J = 25.8 Hz, CH), 108.6 (d, J = 7.1 Hz,
CH), 114.1 (CH), 119.1 (CH2), 125.4 (d, J = 2.7 Hz, C), 130.2 (d,
J = 7.7 Hz, CH), 134.7 (CH), 155.3 (d, J = 267.6 Hz, C), 159.1 (d,
J = 2.7 Hz, C) ppm. MS (EI): m/z = 312.00 [M+H]+. Elemental
analysis for C16H22FNO2S: calcd: C, 61.71; H, 7.12; N, 4.50; S,
10.30. Found: C, 61.57; H, 7.00; N, 4.38; S, 10.23.
Dia 2: Yellow solid. Rf 0.3 (PE/EtOAc: 1/1). IR (KBr): n
3183, 2957, 1685, 1607, 1512, 1367, 1300, 1249, 1181, 1057, 925,
856 cm-1. 1H NMR (CDCl3, 300 MHz): d 1.24 (s, 9H), 3.59 (d, J =
4.7 Hz, 1H), 3.79 (s, 3H), 4.49–4.59 (m, 1H), 5.36 (d, J = 10.2 Hz,
1H), 5.45 (d, J = 17.1 Hz, 1H), 5.73 (d, J = 39.2 Hz, 1H), 5.84–5.95
(m, 1H), 6.85 (d, J = 8.7 Hz, 2H), 7.44 (d, J = 8.8 Hz, 2H) ppm.
19F NMR (CDCl3, 282.5 MHz): d -117.6 (dd, J = 16.5 Hz, J =
39.2 Hz) ppm. 13C NMR (CDCl3, 75.4 MHz): d 22.7 (CH3), 55.3
(CH3), 56.2 (C), 59.7 (d, J = 27.4 Hz, CH), 108.0 (d, J = 7.1 Hz,
CH), 114.0 (CH), 119.7 (CH2), 125.2 (d, J = 2.7 Hz, C), 130.3 (d, J
= 7.7 Hz, CH), 134.2 (d, J = 1.64 Hz, CH), 156.2 (d, J = 267.6 Hz,
C), 159.1 (d, J = 2.7 Hz, C) ppm. MS (EI): m/z = 312.00 [M+H]+.
Elemental analysis for C16H22FNO2S: calcd: C, 61.71; H, 7.12; N,
4.50; S, 10.30. Found: C, 61.50; H, 6.98; N, 4.42; S, 10.25.
Product of imine reduction from 5
N-[(Z)-2-Fluoro-3-(4-methoxyphenyl)-2-propenyl]-2-methyl-2-
propanesulfinamide. Yellow solid. Rf 0.25 (PE/EtOAc: 1/1). IR
(KBr): 2931, 1697, 1608, 1513, 1459, 1325, 1298, 1253, 1180, 1028,
819, 692, 560 cm-1. 1H NMR (CDCl3, 300 MHz): d 1.23 (s, 9H),
3.53 (6, J = 6.2 Hz, 1H), 3.82 (s, 3H), 3.86 (ddd, J = 6.4 Hz, J =
16.0 Hz, J = 12.8 Hz, 2H), 5.76 (d, J = 38.4 Hz, 1H), 6.85 (d, J
= 8.7 Hz, 2H), 7.43 (d, J = 8.7 Hz, 2H) ppm. 19F NMR (CDCl3,
282.5 MHz): d -113.1 (dt, J = 15.5 Hz, J = 39.2 Hz) ppm. 13C
NMR (CDCl3, 75.4 MHz): d 22.6 (CH3), 47.2 (d, J = 30.2 Hz,
CH2), 55.3 (CH3), 56.3 (C), 108.2 (d, J = 7.1 Hz, CH), 114.0 (CH),
125.4 (d, J = 3.3 Hz, C), 130.1 (d, J = 7.1 Hz, CH), 155.0 (d, J =
264.3 Hz, C), 159.0 (d, J = 2.7 Hz, C) ppm. MS (EI): m/z = 286.13
[M+H]+. Elemental analysis for C14H20FNO2S: C: 58.92, H: 7.06,
N: 4.91; S, 11.24. Found: C: 58.86, H: 6.95, N: 4.84; S, 11.20.
N-{1-[(Z)-1-Fluoro-2-(4-methoxyphenyl)ethenyl]-3-butenyl}-2-
methyl-2-propanesulfinamide (7f). Dia 1: Yellow solid. Rf 0.38
1
(PE/EtOAc: 1/1). H NMR (CDCl3, 300 MHz): d 1.23 (s, 9H),
2.47–2.61 (m, 1H), 3.56 (J = 7.0 Hz, 1H), 3.80 (s, 3H), 3.86–4.04
(m, 1H), 5.11–5.20 (m, 2H), 5.75 (d, J = 39.5 Hz, 1H), 5.70–5.83
(m, 1H), 6.85 (d, J = 8.9 Hz, 2H), 7.44 (d, J = 8.9 Hz, 2H) ppm 19
F
NMR (CDCl3, 282.5 MHz): d -120.2 (dd, J = 19.6 Hz, J = 40.2
Hz) ppm.
Dia 2: Yellow solid. Rf 0.26 (PE/EtOAc: 1/1). IR (KBr): n 3199,
2946, 2868, 1686, 1610, 1514, 1444, 1300; 1255, 1180, 1055, 916,
856, 811 cm-1. 1H NMR (CDCl3, 300 MHz): d 1.19 (s, 9H), 2.47–
2.66 (m, 1H), 3.48 (J = 3.6 Hz, 1H), 3.77 (s, 3H), 3.95–4.07 (m,
1H), 5.15–5.22 (m, 2H), 5.67 (d, J = 39.4 Hz, 1H), 5.69–5.83 (m,
1H), 6.84 (d, J = 8.9 Hz, 2H), 7.41 (d, J = 8.9 Hz, 2H) ppm. 19F
NMR (CDCl3, 282.5 MHz): d -121.2 (dd, J = 19.6 Hz, J = 39.2
Hz) ppm. 13C NMR (CDCl3, 75.4 MHz): d 22.5 (CH3), 38.0 (CH2),
55.2 (CH3), 55.9 (C), 56.3 (CH), 108.2 (d, J = 7.1 Hz, CH), 113.9
(CH), 119.7 (CH2), 125.3 (d, J = 2.7 Hz, C), 130.0 (d, J = 7.7 Hz,
CH), 133.0 (CH), 156.0 (d, J = 267.1 Hz, C), 158.8 (d, J = 3.3 Hz,
C) ppm. MS (EI): m/z = 326.33 [M+H]+. Elemental analysis for
C17H24FNO2S: C, 62.74; H, 7.43; N, 4.30; S, 9.85. Found: C, 62.56;
H, 7.36; N, 4.15; S, 9.80.
N-((Z)-5-{[tert-Butyl(diphenyl)silyl]oxy}-2-fluoro-1-phenyl-2-
pentenyl)-2-methyl-2-propanesulfinamide (8a). Dia 1: Yellow oil.
Rf 0.17 (Cyclohexane/EtOAc: 7/3). IR (KBr): n 2930, 2858, 1707,
1
1473, 1428, 1362.9, 1111, 1056, 937, 823, 702 cm-1. H NMR
(CDCl3, 300 MHz): d 1.02 (s, 9H), 1.23 (s, 9H), 2.34–2.40 (m, 2H),
3.66 (t, J = 6.2 Hz, 2H), 3.73 (d, J = 3.9 Hz, 1H), 4.98 (dt, J =
7.3 Hz, J = 36.9 Hz, 1H), 5.01–5.07 (m, 1H), 7.30–7.41 (m, 6H),
7.62–7.67 (m, 4H) ppm. 19F NMR (CDCl3, 282.5 MHz): d -119.2
(dd, J = 15.8 Hz, J = 37.1 Hz) ppm. 13C NMR (CDCl3, 75.4 MHz):
d 19.2 (C), 22.6 (CH3), 26.9 (CH3), 27.3 (d, J = 3.6 Hz, CH2), 56.1
(C), 60.1 (d, J = 29.0 Hz, CH), 62.9 (d, J = 1.6 Hz, CH2), 106.4
(d, J = 13.1 Hz, CH), 127.6 (CH), 128.5 (CH), 128.9 (CH), 129.6
(CH), 134.6 (C), 135.6 (CH), 138.6 (C), 157.1 (d, J = 258.4 Hz,
C) ppm. MS (EI): m/z = 537.93 [M+◦]. Elemental analysis for
C31H40FNO2SSi: calcd: C, 69.23; H, 7.50; N, 2.60; S, 5.95. Found:
C, 69.18; H, 7.68; N, 2.39; S, 5.90.
N-[(Z)-2-Fluoro-3-(4-methoxyphenyl)-1-vinyl-2-propenyl]-2-
methyl-2-propanesulfinamide (7g). Dia 1: Yellow solid. Rf 0.4
(PE/EtOAc: 1/1). IR (KBr): n 3183, 2957, 1685, 1607, 1512, 1367,
1
1300, 1249, 1181, 1057, 925, 856 cm-1. H NMR (CDCl3, 300
MHz): d 1.24 (s, 9H), 3.36 (d, J = 5.1 Hz, 1H), 3.81 (s, 3H), 4.55
(ddd, J = 5.2 Hz, J = 6.4 Hz, J = 18.3 Hz, 1H), 5.34 (d, J = 10.2 Hz,
1H), 5.47 (d, J = 16.9 Hz, 1H), 5.73 (d, J = 38.8 Hz, 1H), 5.97–6.09
(m, 1H), 6.86 (d, J = 8.6 Hz, 2H), 7.44 (d, J = 8.8 Hz, 2H) ppm.
Dia 2: Yellow oil. 19F NMR (CDCl3, 282.5 MHz): d -121.4 (dd,
J = 16.5 Hz, J = 37.1 Hz) ppm.
2384 | Org. Biomol. Chem., 2011, 9, 2378–2386
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The Royal Society of Chemistry 2011
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