Oxidative Fragmentations of 2-(Trimethylsilyl)ethyl Sulfoxides
FULL PAPER
(SϭO stretch 1138 cmϪ1). Addition of 3-phenyl-1-propanol (194
1603, 1581, 1497, 1454, 1168, 1125, 1004, 901, 834, 772 cmϪ1. Ϫ
µL, 1.43 mmol) and K2CO3 (880 mg, 6.37 mmol) afforded sulfinate MS (CI, NH3); m/z (%): 183 (2), 119 (14), 118 (27), 105 (7), 92 (5),
ester 13d (238 mg, 52%) as an oil after flash chromatography (7% 91 (100), 77 (14), 65 (10). Ϫ C11H13ClO2S (244.7): calcd. C 53.98,
EtOAc/hexanes). Ϫ 1H NMR (400 MHz): δ ϭ 7.21Ϫ7.16 (m, 2 H),
7.12Ϫ7.08 (m, 3 H), 6.59 (s, 1 H), 4.00 (t of AB q, J ϭ 10.0, 6.4 Hz,
2 H), 2.64 (t, J ϭ 7.2 Hz, 2 H), 1.99Ϫ1.91 (m, 2 H), 0.16 (s, 9 H).
H 5.35; found C 53.70, H 5.09.
Synthesis of 3-Phenylpropyl (Z)-2-Chloroethenesulfinate (14d): The
reaction of sulfoxide 9d (383 mg, 2.04 mmol) with SO2Cl2
(1.28 mL, 1.28 mmol) provided the sulfinyl chloride (SϭO stretch
1154 cmϪ1). Addition of 3-phenyl-1-propanol (280 µL, 2.04 mmol)
and K2CO3 (704 mg, 5.09 mmol) afforded sulfinate ester 14c
(143 mg, 32%, from sulfoxide) as an oil and 14d (123 mg, 27%,
from sulfoxide) as an oil that could not be completely purified us-
Ϫ
13C NMR (100.6 MHz): δ ϭ 149.8, 144.8, 140.8, 128.4 (2 C),
126.0, 66.7, 31.7, 31.5, Ϫ2.7. Ϫ IR (film): 3027, 3004, 2956, 1604,
1568, 1497, 1455, 1382, 1252, 1188, 1124, 1121, 1006, 920 cmϪ1. Ϫ
MS (EI); m/z (%): 317 (14) [Mϩ], 119 (55), 118 (84), 117 (36), 105
(28), 104 (17), 103 (30), 91 (100), 83 (25), 79 (25), 78 (22), 77 (31),
75 (22), 74 (23), 73 (88), 65 (38), 63 (17), 51 (18). Ϫ C14H21ClO2SSi
(316.9): calcd. C 53.06, H 6.68; found C 52.87, H 6.67. Ϫ The
reaction of sulfoxide 13d (223 mg, 0.79 mmol) with SO2Cl2
(0.950 mL, 0.95 mmol) provided the sulfinyl chloride (SϭO stretch
1139 cmϪ1). Addition of 3-phenyl-1-propanol (100 µL, 0.75 mmol)
and K2CO3 (438 mg, 3.17 mmol) afforded sulfinate ester 13d
(137 mg, 57%) as an oil after flash chromatography (7% EtOAc/
hexanes).
1
ing flash chromatography (7% EtOAc/hexanes). Ϫ 14d: H NMR
(400 MHz): δ ϭ 7.22Ϫ7.16 (m, 2 H), 7.12Ϫ7.08 (m, 3 H), 6.64 (d,
J ϭ 7.0 Hz, 1 H), 6.53 (d, J ϭ 7.0 Hz, 1 H), 4.06 (m, 1 H), 3.95
(m, 1 H), 2.64 (t, J ϭ 7.2 Hz, 2 H), 1.99Ϫ1.92 (m, 2 H). Ϫ 13C
NMR (100.6 MHz): δ ϭ 140.7, 139.9, 128.4 (2 C), 128.2, 126.1,
66.6, 31.7, 31.5. Ϫ IR (film): 3085, 3028, 2951, 2884, 1574, 1497,
1454, 1249, 1151, 1006 cmϪ1. MS (EI); m/z (%): 245 [18, (Mϩ for
35Cl)], 119 (30), 118 (97), 117 (29), 91 (100), 73 (15). Ϫ HRMS
(EI), calcd. for C11H1435ClO2S: 245.0403; found 245.0403. Ϫ The
reaction of sulfoxide 9d (153 mg, 0.73 mmol) with SO2Cl2
(0.770 mL, 0.77 mmol) provided the sulfinyl chloride. Addition of
3-phenyl-1-propanol (100 µL, 0.77 mmol) and K2CO3 (406 mg,
2.94 mmol) afforded the trans isomer of the sulfinate ester 14c
(60 mg, 34%, from the sulfoxide) as an oil (7% EtOAc/hexanes).
Synthesis of Cyclohexyl (Z)-2-Chloro-2-phenylethenesulfinate (14a):
The reaction of sulfoxide 9a (182 mg, 0.63 mmol) with SO2Cl2 (760
µL, 0.76 mmol) provided the sulfinyl chloride (SϭO stretch
1154 cmϪ1). Addition of cyclohexanol (57 mg, 0.57 mmol) and
K2CO3 (351 mg, 2.53 mmol) afforded sulfinate ester 14a (117 mg,
65%) as an oil after flash chromatography (10% EtOAc/hexanes).
Ϫ
1H NMR (400 MHz): δ ϭ 7.46Ϫ7.36 (m, 5 H), 7.14 (s, 1 H),
Synthesis of Cyclohexyl (E)-1,4-Bis(acetoxy)-3-chloro-2-but-2-ene-
sulfinate (15a): The reaction of sulfoxide 10a (245 mg, 0.69 mmol)
with SO2Cl2 (0.83 mL, 0.83 mmol) provided the sulfinyl chloride
(SϭO stretch 1156 cmϪ1). Addition of cyclohexanol (75 mg,
0.75 mmol) and K2CO3 (207.mg, 1.50 mmol) afforded sulfinate es-
ter 15a (130 mg, 53%) after flash chromatography (10% EtOAc/
hexanes) and several water washes of the chromatographic frac-
4.21 (m, 1 H), 1.80 (m, 1 H), 1.63 (m, 2 H), 1.47 (m, 3 H), 1.21
(m, 4 H). Ϫ 13C NMR (100.6 MHz): δ ϭ 148.1, 129.8, 129.2, 128.9,
128.6, 126.5, 79.4, 33.3, 32.9, 24.9, 23.5, 23.3. Ϫ IR (film): 3063,
3033, 3005, 2959, 2911, 2836, 1610, 1513, 1455, 1303, 1251, 1178,
1032, 909 cmϪ1. Ϫ MS (EI); m/z (%): 284 (3) [Mϩ], 205 (41), 204
(20), 203 (90), 185 (21), 139 (33), 138 (32), 137 (77), 102 (100), 101
(28), 83 (97), 77 (21), 67 (21), 55 (85), 51 (20). Ϫ C14H17ClO2S
(284.8): calcd. C 59.04, H 6.02; found C 58.83, H 5.92.
1
tions, which also contained cyclohexanol. Ϫ H NMR (400 MHz):
δ ϭ 5.04 (s, 2 H), 5.02 (AB q, J ϭ 12.6 Hz, 2 H), 4.28 (m, 1 H),
2.13 (s, 3 H), 2.07 (s, 3 H), 1.92 (m, 2 H), 1.73 (m, 2 H), 1.51 (m,
1.52) 1.49Ϫ1.24 (m, 2 H). Ϫ 13C NMR (100.6 MHz): δ ϭ 170.3,
169.9, 144.1, 141.9, 79.3, 62.0, 55.7, 33.5, 33.0, 25.0, 23.6, 23.6,
20.6, 20.5. Ϫ IR (film): 2938, 2859, 1748, 1633, 1448, 1376, 1224,
1143, 1032 cmϪ1. Ϫ MS (EI); m/z (%): 253 (1) [(M Ϫ C6H11O) ϩ
H]ϩ, 211 (19), 146 (59), 111 (49), 104 (81), 92 (47), 91 (61), 86 (60),
85 (64), 84 (100), 60 (35), 52 (89). Ϫ C14H21ClO6S (352.8): calcd.
C 47.66, H 6.00; found C 47.42, H 5.81.
Synthesis of 3-Phenylpropyl (E)-2-Butyl-2-chloroethenesulfinate
(14b): The reaction of sulfoxide 9b (116 mg, 0.43 mmol) with
SO2Cl2 (521 µL, 0.52 mmol) provided the sulfinyl chloride (SϭO
stretch 1154 cmϪ1). Addition of 3-phenyl-1-propanol (59.3 µL,
0.44 mmol) and K2CO3 (152 mg, 1.10 mmol) afforded sulfinate es-
ter 14b (87 mg, 67%) as an oil after flash chromatography (7%
EtOAc/hexanes). Ϫ 1H NMR (400 MHz): δ ϭ 7.35Ϫ7.30 (m, 2 H),
7.26Ϫ7.21 (m, 3 H), 6.90 (s, 1 H), 3.95 (t of AB q, J ϭ 9.8, 6.4 Hz,
2 H), 2.75 (t, J ϭ 7.6 Hz, 2 H), 2.62Ϫ2.54 (m, 1 H), 2.42Ϫ2.34 (m,
1 H), 2.08Ϫ2.01 (m, 2 H), 1.64Ϫ1.57 (m, 2 H), 1.44 (sext, J ϭ
7.4 Hz, 2 H), 0.98 (t, J ϭ 7.4 Hz, 3 H). Ϫ 13C NMR (100.6 MHz):
δ ϭ 148.3, 140.8, 128.5, 128.4, 126.8, 126.1, 64.9, 31.9, 31.4, 29.6,
25.4, 22.6, 13.7. Ϫ IR (film): 3027, 2957, 2932, 2873, 2863, 1625,
1601, 1466, 1454, 1139, 1007 cmϪ1. Ϫ MS (CI, NH3); m/z (%): 301
(32) [(M ϩ H)ϩ], 183 (29), 165 (25), 119 (100), 118 (45), 117 (26),
91 (79), 81 (21), 57 (25), 59 (45). Ϫ C15H21ClO2S (300.8): calcd. C
59.89, H 7.04; found C 59.70, H 6.94.
Synthesis of Cyclohexyl (E)-4-Chloro-3-hex-3-enesulfinate (15b):
The reaction of sulfoxide 10b (128 mg, 0.48 mmol) with SO2Cl2
(0.60 mL, 0.60 mmol) provided the sulfinyl chloride (SϭO stretch
1153 cmϪ1). Addition of cyclohexanol (35 mg, 0.35 mmol) and
K2CO3 (249 mg, 1.80 mmol) afforded sulfinate ester 15b (99 mg,
78%) after flash chromatography (7% EtOAc/hexanes). Ϫ 1H NMR
(400 MHz): δ ϭ 4.21 (m, 1 H), 2.79Ϫ2.61 (m, 3 H), 2.54Ϫ2.45 (m,
1 H), 1.93 (m, 2 H), 1.74 (m, 2 H), 1.58Ϫ1.50 (m, 2 H), 1.39Ϫ1.24
(m, 2 H), 1.20 (t, J ϭ 7.5 Hz, 3 H), 1.17 (t, J ϭ 7.6 Hz, 3 H). Ϫ
13C NMR (100.6 MHz): δ ϭ 145.4, 144.9, 78.1, 33.7, 33.0, 28.9,
25.1, 23.7, 23.6, 18.3, 13.4, 12.7. Ϫ IR (film): 2977, 2935, 2859,
1630, 1454, 1371, 1141, 934 cmϪ1. Ϫ MS (EI); m/z (%): 264 (2,
Mϩ), 185 (29), 183 (78), 167 (18), 165 (16), 83 (100), 82 (21), 81
(25), 67 (31), 55 (64). Ϫ C12H21ClO2S (264.8): calcd. C 54.43, H
7.99; found C 54.19, H 8.08.
Synthesis of 3-Phenylpropyl (E)-2-Chloroethenesulfinate (14c): The
reaction of sulfoxide 9c (200 mg, 0.95 mmol) with SO2Cl2 (670 µL,
0.67 mmol) provided sulfinyl chloride (SϭO stretch 1133 cmϪ1).
Addition of 3-phenyl-1-propanol (120 µL, 0.91 mmol) and K2CO3
(331 mg, 2.39 mmol) afforded sulfinate ester 14c (133 mg, 57%) as
an oil after flash chromatography (7% EtOAc/hexanes). Ϫ 1H
NMR (400 MHz): δ ϭ 7.32Ϫ7.29 (m, 2 H), 7.23Ϫ7.18 (m, 3 H),
6.97 (d, J ϭ 13.2 Hz, 1 H), 6.68 (d, J ϭ 13.2 Hz, 1 H), 4.01 (t of Synthesis of 3-Phenylpropyl 1,2-Dichloropropanesulfinate (16): The
AB q, J ϭ 10.0, 6.4 Hz, 1 H), 2.73 (t, J ϭ 7.6 Hz, 2 H), 2.03 (m, reaction of sulfoxide 11 (132 mg, 0.69 mmol) with SO2Cl2 (902 µL,
2 H). Ϫ 13C NMR (100.6 MHz): δ ϭ 140.7, 137.9, 132.3, 128.5,
0.90 mmol) provided sulfinyl chloride (SϭO stretch 1145 cmϪ1).
128.4, 126.1, 65.0, 31.8, 31.3. Ϫ IR (film): 3062, 3027, 2950, 2886, Addition of 3-phenyl-1-propanol (89 µL, 0.66 mmol) and K2CO3
Eur. J. Org. Chem. 2001, 1643Ϫ1654 1653