December 2006
1737
150 (49), 149 (47), 135 (100), 105 (28), 91 (24), 77 (8), 59 (49). Calcd for
C12H16OS: M, 208.0921. Found: m/z 208.0921.
2.48—2.61 (4H, m), 3.77 (3H, s), 6.39 (1H, t, Jꢀ6.7 Hz), 6.77 (2H, d,
Jꢀ8.9 Hz), 6.99 (2H, d, Jꢀ8.9 Hz), 7.01 (2H, d, Jꢀ8.0 Hz), 7.07 (2H, d,
Jꢀ8.0 Hz); MS m/z (%) 382 (Mꢂ, 53), 261 (27), 243 (29), 149 (27), 137
(56), 121 (100), 119 (19), 91 (19). Calcd for C24H30O2S: M, 382.1966.
Found: m/z 382.1971.
4j: Colorless oil. IR (neat) 3296 (OH), 2927, 2854, 1491, 1458, 808 cmꢁ1
;
1H-NMR d 1.32—1.38 (26H, m), 1.63—1.69 (2H, m), 1.80—1.86 (2H, m),
1.93 (1H, s, OH), 2.35 (3H, s), 4.67 (1H, d, Jꢀ0.9 Hz), 5.26 (1H, d,
Jꢀ0.9 Hz), 7.16 (2H, d, Jꢀ7.9 Hz), 7.36 (2H, d, Jꢀ7.9 Hz); MS m/z (%) 374
(Mꢂ, 100), 251 (7), 225 (4), 150 (35), 124 (12), 105 (10), 91 (7). Calcd for
C24H38OS: M, 374.2643. Found: m/z 374.2659.
The Allylic Alcohols 4b—m in Table 1 4b: E-4b; colorless oil. IR
1
(neat) 3481 (OH), 2929, 1615, 1515, 1246, 1104, 1036, 965, 808 cmꢁ1; H-
NMR d 1.52—1.63 (4H, m), 1.91 (2H, dt, Jꢀ13.5, 4.0 Hz), 2.16 (2H, dt,
Jꢀ13.5, 4.0 Hz), 2.32 (3H, s), 2.62 (2H, t, Jꢀ7.3 Hz), 2.73 (2H, q,
Jꢀ7.6 Hz), 3.79 (3H, s), 3.93 (4H, t, Jꢀ2.8 Hz), 5.77 (1H, t, Jꢀ8.0 Hz),
6.18 (2H, d, Jꢀ8.3 Hz), 7.07 (4H, d, Jꢀ8.9 Hz), 7.16 (2H, d, Jꢀ8.0 Hz); MS
m/z (%) 440 (Mꢂ, 46), 319 (28), 301 (11), 195 (69), 151 (16), 121 (100), 99
(23). Calcd for C26H32O4S: M, 440.2022. Found: m/z 440.2026. Z-4b; color-
4k: Colorless oil. IR (neat) 3400 (OH), 2928, 1599, 1490, 1366, 1119,
1
804 cmꢁ1; H-NMR d 1.49 (6H, s), 2.04 (3H, s), 2.15 (3H, s), 2.28 (3H, s),
2.53 (1H, s, OH), 7.05 (4H, s). MS m/z (%) 236 (Mꢂ, 96), 218 (21), 203
(14), 178 (100), 163 (58), 143 (32), 133 (33), 105 (21), 91 (30). Calcd for
C14H20OS: M, 236.1234. Found: m/z 236.1234.
less oil. IR (neat) 3480 (OH), 2928, 1514, 1247, 1096, 1036, 980, 806 cmꢁ1
;
4l: Colorless oil. IR (neat) 3468 (OH), 2928, 1596, 1491, 1375, 1099,
1
1035, 805, 768 cmꢁ1; H-NMR d 1.54—1.60 (2H, m), 1.67—1.71 (2H, m),
1H-NMR d 1.57—1.78 (4H, m), 1.89—2.01 (4H, m), 2.10 (1H, s), 2.27 (3H,
s), 2.50—2.60 (4H, m), 3.77 (3H, s), 3.91—3.97 (4H, m), 6.40 (1H, t,
Jꢀ7.0 Hz), 6.78 (2H, d, Jꢀ8.3 Hz), 7.00 (4H, t, Jꢀ8.3 Hz), 7.06 (4H, d,
Jꢀ8.3 Hz); MS m/z (%) 440 (Mꢂ, 26), 319 (22), 301 (11), 257 (7), 239 (4),
195 (42), 151 (14), 121 (100), 99 (24), 91 (13). Calcd for C26H32O4S: M,
440.2021. Found: m/z 440.2021.
1.97 (2H, dt, Jꢀ13.2, 4.3 Hz), 2.05 (3H, s), 2.19 (3H, s), 2.28 (3H, s), 2.32
(2H, dt, Jꢀ13.2, 4.3 Hz), 2.33 (1H, s, OH), 3.93 (4H, t, Jꢀ2.1 Hz), 7.04
(4H, s). MS m/z (%) 334 (Mꢂ, 52), 316 (29), 178 (100), 163 (28), 149 (27),
124 (20), 101 (73), 91 (32). Calcd for C19H26O3S: M, 334.1601. Found: m/z
334.1611.
4m: Colorless oil. IR (neat) 3468 (OH), 2927, 2856, 1491, 1447, 1258,
4c: E-4c; colorless oil. IR (neat) 3504 (OH), 2925, 1511, 1247, 805,
1
1084, 803 cmꢁ1; H-NMR d 1.50—1.53 (2H, m), 1.56—1.66 (4H, m), 1.71
1
701 cmꢁ1; H-NMR d 2.29 (3H, s), 2.24—2.51 (4H, m), 3.67 (1H, s, OH),
(2H, d, Jꢀ12.5 Hz), 1.90—1.97 (3H, m), 2.03 (3H, s), 2.21 (3H, s), 2.28
(3H, s), 7.03 (4H, s). MS m/z (%) 276 (Mꢂ, 51), 258 (33), 178 (100), 163
(27), 143 (12), 133 (16), 107 (20), 91 (31). Calcd for C17H24OS: M,
276.1546. Found: m/z 276.1544.
3.80 (3H, s), 5.63 (1H, t, Jꢀ7.1 Hz), 6.79 (2H, d, Jꢀ8.5 Hz), 6.91 (2H, d,
Jꢀ8.5 Hz), 7.04 (2H, d, Jꢀ8.0 Hz), 7.16 (2H, d, Jꢀ8.0 Hz), 7.20—7.22 (4H,
m), 7.24—7.31 (8H, m); MS m/z (%) 466 (Mꢂ, 38), 284 (41), 221 (24), 191
(32), 163 (37), 121 (100), 105 (63), 77 (21). Calcd for C31H30O2S: M,
466.1964. Found: m/z 466.1968. Z-4c; colorless oil. IR (neat) 3472 (OH),
Allylic Alcohol 4n and a-Sulfanyl Ketones 5n, 5o, and 5p in Table 2
4n: Colorless oil. IR (neat) 3419 (OH), 1679, 1448, 1233, 1019, 950,
1
3023, 2922, 1612, 1514, 1447, 1246, 1178, 1035, 809, 762, 701 cmꢁ1; H-
1
799 cmꢁ1; H-NMR d 2.34 (3H, s), 5.04 (1H, s), 5.27 (1H, s), 5.51 (1H, s),
NMR d 1.72 (2H, q, Jꢀ7.4 Hz), 2.26 (2H, t, Jꢀ7.7 Hz), 2.33 (3H, s), 3.54
(1H, s, OH), 3.77 (3H, s), 5.95 (1H, t, Jꢀ7.6 Hz), 6.72 (4H, s), 7.07 (2H, d,
Jꢀ8.3 Hz), 7.22 (2H, d, Jꢀ8.3 Hz), 7.26—7.30 (10H, m); MS m/z (%) 466
(Mꢂ, 24), 448 (6), 284 (24), 221 (43), 187 (27), 163 (30), 121 (100), 105
(64). Calcd for C31H30O2S: M, 466.1964. Found: m/z 466.1962.
7.13 (2H, d, Jꢀ7.9 Hz), 7.30—7.32 (3H, m), 7.34—7.37 (2H, m), 7.41 (2H,
d, Jꢀ7.9 Hz). MS m/z (%) 256 (Mꢂ, 100), 246 (7), 150 (37), 149 (53), 135
(61), 115 (15), 105 (63), 91 (30). Calcd for C16H16OS: M, 256.0920. Found:
m/z 256.0918.
5n30): Colorless oil. IR (neat) 2926, 1681 (CO), 1448, 1233, 1178, 950,
4d: E-4d; colorless oil. IR (neat) 3401 (OH), 2982, 2940, 1513, 1247,
1
812, 718 cmꢁ1; H-NMR d 1.50 (3H, d, Jꢀ6.8 Hz), 2.31 (3H, s), 4.55 (1H,
1036, 732 cmꢁ1 1H-NMR d 1.38 (6H, s), 1.95 (1H, s, OH), 2.32 (3H, s),
;
q, Jꢀ6.8 Hz), 7.07 (2H, d, Jꢀ8.0 Hz), 7.21—7.24 (2H, m), 7.43 (2H, t,
Jꢀ7.6 Hz), 7.54 (1H, m), 7.95 (2H, m) . MS m/z (%) 256 (Mꢂ, 33), 151
(100), 123 (25), 105 (29), 91 (8), 77 (27). Calcd for C16H16OS: M, 256.0920.
Found: m/z 256.0912.
2.60—2.73 (4H, m), 3.79 (3H, s), 5.72 (1H, t, Jꢀ7.5 Hz), 6.82 (2H, d,
Jꢀ8.5 Hz), 7.05 (2H, d, Jꢀ8.5 Hz), 7.08 (2H, d, Jꢀ8.0 Hz), 7.18 (2H, d,
Jꢀ8.0 Hz); MS m/z (%) 342 (Mꢂ, 51), 221 (48), 203 (22), 149 (37), 121
(100), 97 (79), 91 (16). Calcd for C21H26O2S: M, 342.1652. Found: m/z
342.1656. Z-4d; colorless oil. IR (neat) 3448 (OH), 2923, 1511, 1246, 1037,
5o: Colorless oil. IR (neat) 2924, 1713 (CO), 1493, 1454, 1375, 1032,
809 cmꢁ1 1H-NMR d 1.33 (3H, d, Jꢀ7.0 Hz), 2.32 (3H, s), 3.76 (1H, q,
;
805 cmꢁ1 1H-NMR d 1.39 (6H, s), 2.28 (3H, s), 2.52 (2H, t, Jꢀ7.1 Hz),
;
Jꢀ7.0 Hz), 3.88 (1H, d, Jꢀ15.3 Hz), 3.95 (1H, d, Jꢀ15.3 Hz), 7.09 (2H, d,
Jꢀ7.9 Hz), 7.17 (2H, d, Jꢀ7.0 Hz), 7.23—7.25 (3H, m), 7.30 (2H, t,
Jꢀ7.9 Hz). MS m/z (%) 270 (Mꢂ, 22), 151 (100), 147 (12), 123 (17), 91
(36). Calcd for C17H18OS: M, 270.1078. Found: m/z 270.1083.
5p: Colorless oil. IR (neat) 3027, 2926, 1709 (CO), 1493, 1454, 811,
699 cmꢁ1; 1H-NMR d 1.32 (3H, d, Jꢀ7.2 Hz), 2.32 (3H, s), 2.83—2.89 (3H,
m), 3.01—3.06 (1H, m), 3.63 (1H, q, Jꢀ7.2 Hz), 7.07 (2H, d, Jꢀ8.4 Hz),
7.16—7.21 (5H, m), 7.27 (2H, t, Jꢀ7.2 Hz). MS m/z (%) 284 (Mꢂ, 34), 151
(100), 123 (13), 105 (10), 91 (19). Calcd for C18H20OS: M, 284.1235.
Found: m/z 284.1230.
2.59 (2H, t, Jꢀ7.1 Hz), 3.77 (3H, s), 6.40 (1H, t, Jꢀ6.7 Hz), 6.79 (2H, d,
Jꢀ8.6 Hz), 7.00 (2H, d, Jꢀ8.6 Hz), 7.02 (2H, d, Jꢀ8.2 Hz), 7.07 (2H, d,
Jꢀ8.2 Hz); MS m/z (%): 342 (Mꢂ, 54), 221 (50), 203 (23), 149 (37), 121
(100), 97 (68), 91 (14). Calcd for C21H26O2S: M, 342.1652. Found: m/z
342.1652.
4e: Colorless crystals; mp 94—95 °C (AcOEt–hexane); IR (KBr) 3335
(OH), 2925, 2854, 1599, 1447, 1121, 979, 873, 813 cmꢁ1 1H-NMR d
;
1.20—1.29 (1H, m), 1.56—1.84 (9H, m), 2.35 (3H, s), 4.67 (1H, s), 5.41
(1H, s), 7.15 (2H, d, Jꢀ8.0 Hz), 7.36 (2H, d, Jꢀ8.0 Hz); MS m/z (%) 248
(Mꢂ, 100), 150 (72), 149 (27), 135 (65), 99 (35), 81 (41). Calcd for
C15H20OS: M, 248.1235. Found: m/z 248.1235. Anal. Calcd: C, 72.53; H,
8.12; S, 12.91. Found: C, 72.67; H, 8.26; S, 12.99.
References and Notes
1) Block E., “Reactions of Organosulfur Compounds,” Academic Press,
New York, 1978.
2) Simpkins N. S., “Sulphones in Organic Synthesis,” Academic Press,
New York, 1993.
3) Metzner P., Thuillier A., “Sulfur Reagents in Organic Synthesis,” Aca-
demic Press, Lonson, 1994.
4) Page P. (ed.), “Organosulfur Chemistry, Synthetic Aspects,” Academic
Press, Lonson, 1995.
4f: Colorless crystals; mp 81—83 °C (AcOEt–hexane). IR (KBr) 3445
(OH), 2961, 1489, 1096, 950, 811 cmꢁ1 1H-NMR d 1.64—1.67 (2H, m),
;
1.83 (1H, s, OH), 1.84—1.87 (2H, m), 1.98—2.05 (2H, m), 2.07—2.13 (2H,
m), 2.34 (3H, s), 3.93—3.99 (4H, m), 4.72 (1H, s), 5.44 (1H, s) 7.16 (2H, d,
Jꢀ7.9 Hz), 7.35 (2H, d, Jꢀ7.9 Hz); MS m/z (%) 306 (Mꢂ, 97), 278 (23), 150
(30), 135 (26), 105 (26), 99 (100), 91 (19). Calcd for C17H22O3S: M,
306.1289. Found: m/z 306.1289.
1
4g: Colorless oil. IR (neat) 3483 (OH), 2959, 1492, 1105, 810 cmꢁ1; H-
5) Whitham G. H., “Organosulfur Chemistry,” Oxford University Press,
Oxford, 1995.
6) Page P. (ed.), “Organosulfur Chemistry, Synthetic and Stereochemical
Aspects,” Academic Press, Lonson, 1998.
7) Patai S., Rappoport Z., Stirling C. (ed.), “The Chemistry of Sulphones
and Sulphoxides,” John Wiley and Sons, Chicester, 1988.
8) Patai S., Rappoport Z. (ed.), “The Syntheses of Sulphones, Sulphox-
ides and Cyclic Sulphides,” John Wiley and Sons, Chichester, 1994.
9) Mikolajczk M., Drabowicz J., Kielbasinski P., “Chiral Sulfur Reagents,
Applications in Asymmetric and Stereoselective Synthesis,” CRC
Press, Boca Raton, 1997.
NMR d 0.94 (6H, t, Jꢀ7.4 Hz), 1.33—1.42 (4H, m), 1.60—1.66 (2H, m),
1.73—1.79 (2H, m), 2.36 (3H, s), 4.54 (1H, s), 5.23 (1H, s), 7.17 (2H, d,
Jꢀ8.0 Hz), 7.37 (2H, d, Jꢀ8.0 Hz); MS m/z (%): 264 (Mꢂ, 25), 222 (100),
193 (15), 151 (51), 150 (43), 135 (51), 71 (46). Calcd for C16H24OS: M,
264.1546. Found: m/z 264.1547.
4h: Colorless oil. IR (neat) 3505 (OH), 3025, 1491, 1447, 1019, 759,
701 cmꢁ1; 1H-NMR d 2.31 (3H, s), 3.49 (1H, s, OH), 4.98 (1H, s), 5.12 (1H,
s), 7.12 (2H, d, Jꢀ7.9 Hz), 7.19—7.37 (8H, m), 7.43—7.45 (4H, m); MS
m/z (%) 332 (Mꢂ, 35), 191 (15), 183 (77), 150 (100), 135 (18), 105 (77), 77
(39). Calcd for C22H20OS: M, 332.1235. Found: m/z 332.1236.
4i29): Colorless oil. IR (neat) 3401 (OH), 2978, 1492, 1364, 1104,
1
810 cmꢁ1; H-NMR d 1.51 (6H, s), 2.35 (3H, s), 4.61 (1H, s), 5.37 (1H, s),
10) Satoh T., J. Syn. Org. Chem. Jpn., 61, 98—110 (2003).
11) Satoh T., Fukuda, Y., Tetrahedron, 59, 9803—9810 (2003).
7.16 (2H, d, Jꢀ8.0 Hz), 7.36 (2H, d, Jꢀ8.0 Hz); MS m/z (%) 208 (Mꢂ, 87),