Less polar isomer: oil; 1H NMR (300 MHz, CDCl3) d 7.59-7.49
(m, 4 H), 5.92 (dt, J1 = 8.5 Hz, J2 = 1.5 Hz, 1 H), 5.26-5.12 (m, 1
H), 3.04 (s, 1 H), 2.42-2.24 (m, 1 H), 1.86-1.68 (m, 1 H), 1.42 (d, J =
6.0 Hz, 3 H), 0.91 (t, J = 7.2 Hz, 3 H); 13C NMR (75 MHz, CDCl3)
d 147.4, 141.2, 138.7, 132.1, 126.1, 124.8, 63.5, 24.4, 17.8, 12.0; IR
(neat, cm-1) 3385, 2970, 2928, 1644, 1571, 1469, 1384, 1293, 1263,
1148, 1113, 1066, 1028, 1006; MS (70 eV, EI) m/z (%) 287 (M+–
OH (81Br), 57.03), 285 (M+–OH (79Br), 55.09), 97 (100); Elemental
analysis calcd for C12H15BrO2S: C, 47.53; H, 4.99; Found: C, 47.53;
H, 5.07.
254 nm, tR = 12.535 min (minor), 13.179 min (major)), [a]2D0 = +96.8
(c = 0.720, CHCl3); solid; m.p. 38–40 ◦C (n-hexane–diethyl ether);
1H NMR (300 MHz, CDCl3) d 7.75-7.62 (m, 2 H), 7.54-7.41 (m, 3
H), 6.23-6.08 (m, 2 H), 4.92-4.78 (m, 1 H), 3.04 (s, 1 H), 1.73-1.52
(m, 2 H), 1.52-1.19 (m, 6 H), 0.88 (t, J = 6.6 Hz, 3 H); 13C NMR
(75 MHz, CDCl3) d 143.8, 142.9, 136.6, 130.8, 129.3, 124.4, 68.8,
37.3, 31.6, 24.8, 22.5, 14.0; IR (KBr) n/cm-1 3363, 3059, 2967,
2930, 2858, 1740, 1615, 1582, 1476, 1464, 1444, 1378, 1305, 1227,
1123, 1083, 1017; MS (70 eV, EI) m/z (%) 253 (M+H+, 0.07), 252
(M+, 0.03), 235 (M+–OH), 100.00); Elemental analysis calcd for
C14H20O2S: C, 66.63; H, 7.99; Found: C, 66.84; H, 8.04.
1
More polar isomer: oil; H NMR (300 MHz, CDCl3) d 7.65-
7.58 (m, 2 H), 7.40-7.33 (m, 2 H), 5.99 (dt, J1 = 9.0 Hz, J2 = 1.8 Hz,
1 H), 5.38-5.25 (m, 1 H), 3.97 (d, J = 2.4 Hz, 1 H), 2.43-2.26 (m, 1
H), 1.85-1.64 (m, 1 H), 1.38 (d, J = 6.3 Hz, 3 H), 0.94 (t, J = 7.2 Hz,
3 H); 13C NMR (75 MHz, CDCl3): d 145.1, 141.1, 140.5, 132.3,
125.9, 125.0, 62.9, 23.0, 17.7, 12.1; IR (neat, cm-1) 3388, 2971,
2929, 1643, 1571, 1468, 1384, 1289, 1152, 1112, 1066, 1041, 1006;
MS (70 eV, EI) m/z (%) 287 (M+–OH (81Br), 43.08), 285 (M+–OH
(79Br), 40.88), 43 (100); Elemental analysis calcd for C12H15BrO2S:
C, 47.53; H, 4.99; Found: C, 47.68; H, 5.14.
More polar isomer: 96.5% ee determined by HPLC analysis
(Chiralcel OJ–H, n-hexane–i-PrOH = 90 : 10, 0.5 mL min-1, l =
254 nm, tR = 11.131 min (major), 12.092 min (minor)), [a]2D0 = -96.9
(c = 1.060, CHCl3); solid; m.p. 78–80 ◦C (n-hexane–diethyl ether);
1H NMR (300 MHz, CDCl3) d 7.73-7.57 (m, 2 H), 7.57-7.44 (m,
3 H), 6.25-6.14 (m, 2 H), 5.00-4.85 (m, 1 H), 4.21 (d, J = 3.9 Hz,
1 H), 1.78-1.61 (m, 1 H), 1.57-1.40 (m, 2 H), 1.40-1.18 (m, 5 H),
0.88 (t, J = 5.9 Hz, 3 H); 13C NMR (75 MHz, CDCl3) d 144.2,
143.5, 135.6, 131.1, 129.4, 124.4, 67.9, 36.6, 31.6, 25.0, 22.5, 14.0;
IR (neat, cm-1) 3374, 3056, 3031, 2955, 2925, 2905, 2870, 2856,
1467, 1442, 1422, 1384, 1320, 1304, 1126, 1084, 1069, 1042; MS
(70 eV, EI) m/z (%) 253 (M+H+, 0.11), 252 (M+, 0.02), 235 (M+–
OH), 100.00); Elemental analysis calcd for C14H20O2S: C, 66.63;
H, 7.99; Found: C, 66.61; H, 7.94.
19. Synthesis of 1-(phenylsulfinyl)non-1(Z)-en-3(R)-ol ((R)-Z-
3c). The reaction of (R)-1c (73.9 mg, 0.30 mmol) in HOAc (3.0
mL) at 60 ◦C for 24 h afforded (R)-Z-3c (20.5 mg (less polar
isomer) and 31.2 mg (more polar isomer), 65%).
Less polar isomer: 98.9% ee determined by HPLC analysis
(Chiralcel OJ-H, n-hexane/–i-PrOH = 95 : 5, 0.5 mL min-1, l =
21. Synthesis of 4-(p-bromophenylsulfinyl)hex-3(Z)-en-2(R)-ol
((R)-Z-3r). The reaction of (R)-1r (84.4 mg, 0.30 mmol) in HOAc
(3.0 mL) at 60 ◦C for 24 h afforded (petroleum–ethyl acetate = 2 : 1)
(R)-Z-3r (26.3 mg (less polar isomer) and 40.1 mg (more polar
isomer), 74%).
254 nm, tR = 19.698 min (minor), 20.923 min (major)), [a]D20
=
+95.8 (c = 0.657, CHCl3); white solid; m.p. 59–61 ◦C (n-hexane–
methylene chloride). 1H NMR (300 MHz, CDCl3) d 7.74-7.62 (m,
2 H), 7.54-7.42 (m, 3 H), 6.24-6.10 (m, 2 H), 4.93-4.80 (m, 1 H),
3.07 (d, J = 4.8 Hz, 1 H), 1.75-1.53 (m, 2 H), 1.53-1.17 (m, 8 H),
0.88 (t, J = 6.8 Hz, 3 H); 13C NMR (75 MHz, CDCl3) d 143.8,
142.9, 136.7, 130.8, 129.3, 124.4, 68.8, 37.4, 31.7, 29.1, 25.1, 22.6,
14.1; IR (KBr) n/cm-1 3358, 3034, 2953, 2922, 2849, 2865, 1612,
1467, 1443, 1316, 1069, 1046, 1004; MS (70 eV, EI) m/z (%) 249
(M+–OH, 100); Elemental analysis calcd for C15H22O2S: C, 67.63;
H, 8.32; Found: C, 67.68; H, 8.31.
Less polar isomer: 95.5% ee determined by HPLC analysis
(Chiralcel OJ–H, n-hexane–i-PrOH = 90 : 10, 0.5 mL min-1, l =
254 nm, tR = 14.281 min (minor), 16.307 min (major)), [a]D20
=
1
+220.5 (c = 0.877, CHCl3); oil; H NMR (300 MHz, CDCl3) d
7.62-7.49 (m, 4 H), 5.92 (d, J = 8.7 Hz, 1 H), 5.26-5.14 (m, 1 H),
2.80 (bs, 1 H), 2.47-2.22 (m, 1 H), 1.86-1.66 (m, 1 H), 1.42 (d, J =
6.3 Hz, 3 H), 0.92 (t, J = 7.4 Hz, 3 H); 13C NMR (75 MHz, CDCl3)
d 147.5, 141.2, 138.6, 132.1, 126.1, 124.8, 63.5, 24.5, 17.7, 12.0;
IR (neat, cm-1) 3382, 3079, 2969, 2928, 2877, 1666, 1645, 1571,
1471, 1385, 1294, 1149, 1113, 1066, 1027, 1006; MS (70 eV, EI)
m/z (%) 287 (M+–OH (81Br), 94.92), 285 (M+–OH (79Br), 91.35),
97 (100); Elemental analysis calcd for C12H15BrO2S: C, 47.53; H,
4.99; Found: C, 47.22; H, 4.94.
More polar isomer: 98.6% ee determined by HPLC analysis
(Chiralcel OJ–H, n-hexane–i-PrOH = 95 : 5, 0.5 mL min-1, l =
254 nm, tR = 13.848 min (major), 15.961 min (minor)), [a]D20
=
◦
-98.0 (c = 1.013, CHCl3); white solid; m.p. 52–54 C (n-hexane–
methylene chloride); 1H NMR (300 MHz, CDCl3) d 7.71-7.58 (m,
2 H), 7.56-7.44 (m, 3 H), 6.25-6.14 (m, 2 H), 4.99-4.86 (m, 1 H),
4.27 (d, J = 3.6 Hz, 1 H), 1.77-1.60 (m, 1 H), 1.60-1.39 (m, 2 H),
1.39-1.18 (m, 7 H), 0.87 (t, J = 6.6 Hz, 3 H); 13C NMR (75 MHz,
CDCl3) d 144.2, 143.4, 135.5, 131.1, 129.4, 124.4, 67.8, 36.6, 31.7,
29.1, 25.3, 22.5, 14.1; IR (KBr) n/cm-1 3373, 3057, 3033, 2953,
2924, 2867, 2854, 1627, 1576, 1469, 1444, 1371, 1314, 1290, 1260,
1125, 1084, 1071, 1041, 1023; MS (70 eV, EI) m/z (%) 249 (M–
OH-, 100); Elemental analysis calcd for C15H22O2S: C, 67.63; H,
8.32; Found: C, 67.63; H, 8.49.
More polar isomer: 94.1% ee determined by HPLC analysis
(Chiralcel OJ–H, n-hexane–i-PrOH = 90 : 10, 0.5 mL min-1, l =
254 nm, tR = 13.593 min (major), 16.710 min (minor)), [a]D20
=
1
-190.2 (c = 1.337, CHCl3); oil; H NMR (300 MHz, CDCl3) d
7.71-7.53 (m, 2 H), 7.42-7.29 (m, 2 H), 5.98 (d, J = 9.3 Hz, 1 H),
5.37-5.21 (m, 1 H), 3.97 (s, 1 H), 2.43-2.22 (m, 1 H), 1.86-1.66
(m, 1 H), 1.36 (d, J = 6.3 Hz, 3 H), 0.92 (t, J = 7.4 Hz, 3 H); 13
C
NMR (75 MHz, CDCl3) d 144.9 141.0, 140.6, 132.3, 125.8, 125.0,
62.8, 22.9, 17.6, 12.0; IR (neat, cm-1) 3390, 3080, 2970, 2928, 2871,
1651, 1570, 1469, 1384, 1289, 1152, 1112, 1078, 1066, 1042, 1006;
MS (70 eV, EI) m/z (%) 287 (M+–OH (81Br), 85.43), 285 (M+–OH
(79Br), 82.61), 97 (100); Elemental analysis calcd for C12H15BrO2S:
C, 47.53; H, 4.99; Found: C, 47.45; H, 5.09.
20. Synthesis of 1-(phenylsulfinyl)oct-1(Z)-en-3(R)-ol ((R)-Z-
3d). The reaction of (R)-1d (118.2 mg, 0.50 mmol) in HOAc (5.0
◦
mL) at 60 C for 24 h afforded (R)-Z-3d (petroleum ether/ethyl
acetate = 2/1) (38.7 mg (less polar isomer) and 46.6 mg (more
polar isomer), 68%).
Less polar isomer: 97.7% ee determined by HPLC analysis
(Chiralcel OJ–H, n-hexane/i-PrOH = 90/10, 0.5 mL min-1, l =
22. Synthesis of 2-deuterium-3-ethyl-1-phenyl-1-(phenyl-
sulfinyl)pent-1(Z)-en-3-ol (Z-3h-D). The reaction of 1h
4560 | Org. Biomol. Chem., 2010, 8, 4554–4561
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