7830 J . Org. Chem., Vol. 63, No. 22, 1998
Schwan et al.
yielded sulfinyl chloride 2d . IR (CH2Cl2), cm-1: 1338, 1147.
Addition of 3-phenylpropanol (89.3 mg, 0.656 mmol) and K2-
CO3 (453 mg, 3.28 mmol) afforded sulfinate 5d (136 mg, 78%)
as an oil after chromatography (7% EtOAc/hexanes). 1H NMR
(400 MHz), δ: 7.24 (m, 5H), 6.51 (d, J ) 15.6 Hz, 1H), 6.17 (d,
J ) 15.6 Hz, 1H), 3.98 (t of ABq, J ) 6.4 & 10.1 Hz, 2H), 2.72
(t, J ) 7.6 Hz, 2H), 2.02 (m, 2H), 1.10 (s, 9H); 13C NMR (100.6
MHz), δ: 153.0, 141.0, 131.0, 128.4 (2 C’s), 126.0, 64.9, 34.0,
31.9, 31.5, 28.7; Anal. Calcd for C15H22O2S: C, 67.63; H, 8.32.
Found: C, 67.51; H, 8.08.
Syn th esis of 3-P h en ylp r op yl (E)-3,3-Dim eth yl-1-bu -
ten esu lfin a te (5d ) fr om P MB (E)-(3,3-Dim eth yl-1-bu te-
n yl) Su lfoxid e (4d ). The reaction mixture of sulfoxide 4d
(200 mg, 0.792 mmol) with SO2Cl2 (950 µL, 0.950 mmol)
yielded sulfinyl chloride 2d . IR (CH2Cl2), cm-1: 3052, 2967,
1338, 1144, 1033. Addition of 3-phenylpropanol (108 mg, 0.792
mmol) and K2CO3 (547 mg, 3.96 mmol) afforded sulfinate 5d
(143 mg, 68%) as an oil after chromatography (7% EtOAc/
hexanes).
Syn th esis of 3-P h en ylp r op yl 1-Cycloh exen esu lfin a te
(5e) fr om DP M 1-Cycloh exen yl Su lfoxid e (3e). The reac-
tion mixture of sulfoxide 3e (161 mg, 0.542 mmol) with SO2-
Cl2 (651 µL, 0.651 mmol) yielded sulfinyl chloride 2e. IR
(CH2Cl2), cm-1: 1451, 1338, 1144. Addition of 3-phenylpro-
panol (73.8 mg, 0.542 mmol) and K2CO3 (375 mg, 2.71 mmol)
afforded sulfinate 5e (119 mg, 83%) as an oil after chroma-
tography (7% EtOAc/hexanes). 1H NMR (400 MHz), δ: 7.24
(m, 5H), 6.51 (m, 1H), 3.94 (t of ABq, J ) 6.4 & 10.1 Hz, 2H),
2.71 (t, J ) 7.7 Hz, 2H), 2.27 (m, 4H), 2.01 (m, 2H), 1.70 (m,
4H); 13C NMR (100.6 MHz), δ: 144.6, 141.0, 133.8, 128.4 (2
C’s), 126.0, 65.3, 31.9, 31.5, 25.2, 21.8, 21.7, 20.3. Anal. Calcd
for C15H20O2S: C, 68.15; H, 7.62. Found: C, 67.97; H, 7.78.
Syn th esis of 3-P h en ylp r op yl 1-cycloh exen esu lfin a te
(5e) fr om P MB 1-Cycloh exen yl Su lfoxid e (4e). The reac-
tion mixture of sulfoxide 4e (150 mg, 0.597 mmol) with SO2-
Cl2 (717 µL, 0.717 mmol) yielded sulfinyl chloride 2e. IR
(CH2Cl2), cm-1: 1338, 1249, 1144, 1034. Addition of 3-phen-
ylpropanol (81.3 mg, 0.597 mmol) and K2CO3 (413 mg, 2.99
mmol) afforded sulfinate 5e (97.9 mg, 62%) as an oil after
chromatography (7% EtOAc/hexanes).
Syn th esis of 3-P h en ylp r op yl 1-P h en yleth en esu lfin a te
(5f) fr om DP M 1-P h en yleth en yl Su lfoxid e (3f). The
reaction mixture of sulfoxide 3f (150 mg, 0.471 mmol) with
SO2Cl2 (565 µL, 0.565 mmol) yielded sulfinyl chloride 2f. IR
(CH2Cl2), cm-1: 1452, 1338, 1216, 1151. Addition of 3-phen-
ylpropanol (64.2 mg, 0.471 mmol) and K2CO3 (326 mg, 2.36
mmol) afforded sulfinate 5f (56.7 mg, 42%) as an oil after
chromatography (5% EtOAc/hexanes). 1H NMR (400 MHz),
δ: 7.24 (m, 10H), 6.17 (s, 1H), 6.05 (s, 1H), 3.87 (t of ABq, J )
6.3 & 10.1 Hz, 2H), 2.51 (t, J ) 7.7 Hz, 2H), 1.85 (m, 2H). 13C
NMR (100.6 MHz), δ: 140.9, 133.6, 129.1, 128.8, 128.4, 128.4
(2 C’s), 126.9, 125.9, 119.8, 64.3, 31.7, 31.2. Anal. Calcd for
Syn th esis of 3-P h en ylp r op yl (E)-2-P h en yleth en esu lfi-
n a te (5g) fr om P MB (E)-2-P h en yleth en yl Su lfoxid e (3g).
The reaction mixture of sulfoxide 3g (174 mg, 0.640 mmol)
with SO2Cl2 (768 µL, 0.768 mmol) yielded sulfinyl chloride 2g.
IR (CH2Cl2), cm-1
: 3054, 1338, 1176, 1149. Addition of
3-phenylpropanol (87.1 mg, 0.640 mmol) and K2CO3 (442 mg,
3.20 mmol) afforded sulfinate 5g (126 mg, 69%) as an oil after
chromatography (10% EtOAc/hexanes).
Syn th esis of 3-P h en ylp r op yl (Z)-2-P h en yleth en esu lfi-
n a te (5h ) fr om DP M (Z)-2-P h en yleth en yl Su lfoxid e (3h ).
The reaction mixture of sulfoxide 3h (195 mg, 0.611 mmol)
with SO2Cl2 (733 µL, 0.733 mmol) yielded sulfinyl chloride 2h .
IR (CH2Cl2), cm-1: 1338, 1130. Addition of 3-phenylpropanol
(83.2 mg, 0.611 mmol) and K2CO3 (422 mg, 3.05 mmol) afforded
sulfinate 5h (97.5 mg, 56%) as an oil after chromatography
(10% EtOAc/hexanes). 1H NMR (400 MHz), δ: 7.27 (m, 10H),
7.10 (d, J ) 11.2 Hz, 1H), 6.45 (d, J ) 11.2 Hz, 1H), 4.09 (t of
ABq, J ) 6.4 & 9.9 Hz, 2H), 2.71 (t, J ) 7.7 Hz, 2H), 2.04 (m,
2H). 13C NMR (100.6 MHz), δ: 140.9, 138.6, 138.4, 133.7,
129.6, 129.5, 128.6, 128.4 (2 C’s), 126.0, 65.7, 31.8, 31.5. Anal.
Calcd for C17H18O2S: C, 71.30; H, 6.34. Found: C, 71.46; H,
6.47.
Syn th esis of 3-P h en ylp r op yl (Z)-2-P h en yleth en esu lfi-
n a te (5h ) fr om P MB (Z)-2-P h en yleth en yl Su lfoxid e (4h ).
The reaction mixture of sulfoxide 4h (116 mg, 0.426 mmol)
with SO2Cl2 (511 µL, 0.511 mmol) yielded sulfinyl chloride 2h .
IR (CH2Cl2), cm-1: 1338, 1129, 1033. Addition of 3-phenyl-
propanol (58.0 mg, 0.426 mmol) and K2CO3 (294 mg, 2.13
mmol) afforded sulfinate 5h (79.3 mg, 65%) as an oil after
chromatography (10% EtOAc/hexanes).
Syn th esis of Cycloh exyl (Z)-2-Ca r bom eth oxyeth en e-
su lfin a te (5i) fr om P MB (Z)-2-Ca r bom eth oxyeth en yl
Su lfoxid e (4i). The reaction of sulfoxide 4i (201 mg, 0.791
mmol) with SO2Cl2 (870 µL, 0.870 mmol) yielded sulfinyl
chloride 2i. IR (CH2Cl2), cm-1: 1724, 1339, 1227, 1159, 1133.
Addition of cyclohexanol (79.2 mg, 0.791 mmol) and K2CO3
(328 mg, 2.37 mmol) afforded sulfinate 5i (89 mg, 48%) as an
unstable oil after chromatography (10% EtOAc/hexanes). 1H
NMR (400 MHz), δ: 6.80 (d, J ) 10.7 Hz, 1H), 6.29 (d, J )
10.7 Hz, 1H), 4.35 (m, 1H), 3.82 (s, 3H), 2.00 (m, 2H), 1.82-
1.21 (m, broad, 8H). 13C NMR (100.6 MHz), δ: 164.1, 153.5,
124.6, 79.5, 52.4, 33.9, 33.1, 25.1, 23.7.
Syn th esis of Eth yl (Z)-2-Ca r bom eth oxyeth en esu lfi-
n a t e (5ii) fr om P MB (E)-2-ca r b om et h oxyet h en yl Su lf-
oxid e (4i). The reaction mixture of sulfoxide (0.500 g, 1.97
mmol) with SO2Cl2 (2.36 mL, 2.36 mmol) yielded sulfinyl
chloride 2i. After addition of absolute ethanol (91 mg, 1.97
mmol) and K2CO3 (1.36 g, 9.85 mmol), the solution was stirred
at -50 °C for 20 h to afford sulfinate 5ii (119 mg, 34%) as an
oil after chromatography on basic alumina (10-20% EtOAc/
hexanes). Kugelrohr distillation of a different sample gave
bp 130 °C/0.5 Torr. 1H NMR (400 MHz), δ: 6.84 (d, J ) 10.4
Hz, 1H), 6.33 (d, J ) 10.4 Hz, 1H), 4.21 (q, J ) 7.1 Hz, 2H),
3.83 (s, 3H), 1.39 (t, J ) 7.1 Hz, 3H). 13C NMR (100.6 MHz),
δ: 164.1, 153.3, 125.5, 64.7, 52.5, 15.9. Anal. Calcd for
C6H10O4S: C, 40.44; H, 5.66. Found: C, 40.57; H, 5.52.
Syn th esis of Cycloh exyl (E)-2-Ca r bom eth oxyeth en e-
su lfin a te (5j) fr om DP M (E)-2-Ca r bom eth oxyeth en yl
Su lfoxid e (3j). The reaction of sulfoxide 3j (199 mg, 0.661
mmol) with SO2Cl2 (793 µL, 0.793 mmol) and warming to -30
°C and stirring overnight yielded sulfinyl chloride 2j. IR (CH2-
Cl2), cm-1: 1736, 1338, 1225, 1164. Addition of cyclohexanol
(66.2 mg, 0.661 mmol) and K2CO3 (457 mg, 3.31 mmol) afforded
sulfinate 5j (57.2 mg, 37%) as an oil after chromatography (7%
EtOAc/hexanes). 1H NMR (400 MHz), δ: 7.41 (d, J ) 15.3
Hz, 1H), 6.58 (d, J ) 15.3 Hz, 1H), 4.29 (m, 1H), 3.78 (s, 3H),
1.91 (m, 2H), 1.73 (m, 2H), 1.53 (m, 3H), 1.37-1.17 (m, 3H).
13C NMR (100.6 MHz), δ: 164.4, 149.8, 127.9, 79.3, 52.4, 33.6,
33.4, 25., 23.7, 23.7. Anal. Calcd for C10H16O4S: C, 51.93; H,
6.54. Found: C, 52.17; H, 6.79.
C
17H18O2S: C, 71.30; H, 6.34. Found: C, 71.53; H, 6.19.
Syn th esis of 3-P h en ylp r op yl 1-P h en yleth en esu lfin a te
(5f) fr om P MB 1-P h en yleth en yl Su lfoxid e (4f). The
reaction mixture of sulfoxide 4f (150 mg, 0.551 mmol) with
SO2Cl2 (826 µL, 0.826 mmol) yielded sulfinyl chloride 2f. IR
(CH2Cl2), cm-1
: 1338, 1152. Addition of 3-phenylpropanol
(75.0 mg, 0.551 mmol) and K2CO3 (381 mg, 2.75 mmol) afforded
sulfinate 5f (109 mg, 69%) as an oil after chromatography (5%
EtOAc/hexanes).
Syn th esis of 3-P h en ylp r op yl (E)-2-P h en yleth en esu lfi-
n a te (5g) fr om DP M (E)-2-P h en yleth en yl Su lfoxid e (3g).
The reaction mixture of sulfoxide 3g (186 mg, 0.584 mmol)
with SO2Cl2 (701 µL, 0.701 mmol) yielded sulfinyl chloride 2g.
IR (CH2Cl2), cm-1: 3055, 1338, 1145. Addition of 3-phenyl-
propanol (79.6 mg, 0.584 mmol) and K2CO3 (404 mg, 2.92
mmol) afforded sulfinate 5g (126 mg, 75%) as an oil after
chromatography (10% EtOAc/hexanes). 1H NMR (400 MHz),
δ: 7.34 (m, 10H), 7.29 (d, J ) 15.9 Hz, 1H), 6.86 (d, J ) 15.9
Hz, 1H), 4.04 (t of ABq, J ) 6.4 & 9.9 Hz, 2H), 2.73 (t, J ) 7.6
Hz, 2H), 2.04 (m, 2H). 13C NMR (100.6 MHz), δ: 140.9, 139.3,
133.2, 132.5, 130.3, 129.0, 128.4 (2 C’s), 128.1, 126.0, 64.9, 31.9,
31.5. Anal. Calcd for C17H18O2S: C, 71.30; H, 6.34. Found:
C, 71.16; H, 6.24.
Syn th esis of Cycloh exyl (E)-2-Ca r bom eth oxyeth en e-
su lfin a te (5j) fr om P MB (E)-2-Ca r bom eth oxyeth en yl
Su lfoxid e (4j). The reaction of sulfoxide 4j (332 mg, 1.31
mmol) with SO2Cl2 (1.57 mL, 1.57 mmol) and warming to room
temperature yielded sulfinyl chloride 2j. IR (CH2Cl2), cm-1
: