4416
M. Watanabe et al. / Tetrahedron 61 (2005) 4409–4418
(19), 189 (33), 151 (17), 147 (16), 105 (22). Calcd for
C15H21O2I: M, 360.0586. Found: m/z 360.0579.
1.33 (9H, s), 1.67 (2H, t, JZ6.6 Hz), 1.70 (2H, t, JZ
6.4 Hz), 2.36 (2H, t, JZ6.4 Hz), 2.48 (2H, t, JZ6.6 Hz),
3.97 (4H, s), 5.87 (1H, s). MS m/z (%) 242 (MC, 52), 186
(63), 153 (100), 124 (18), 99 (25), 86 (40), 57, (39). Calcd
for C13H22O2S: M, 242.1339. Found: m/z 242.1340.
2.1.13. 8-{(p-Tolylsulfanyl)methylene}-1,4-dioxaspiro-
[4.5]decane (20a). To a solution of 17 (65.4 mg;
0.2 mmol) in 6 ml of dry toluene in a flame-dried flask at
K78 8C under argon atmosphere was added t-BuMgCl
(0.025 mmol) dropwise with stirring. After 10 min,
i-PrMgCl (0.60 mmol) was added dropwise to the reaction
mixture at K78 8C to give the magnesium alkylidene
carbenoid 18. n-BuLi (0.66 mmol) was added to a solution
of p-toluenethiol (74.5 mg; 0.6 mmol) in 6 ml of dry toluene
and dry DME (0.21 ml; 2 mmol) in another flame-dried
flask at K78 8C under argon atmosphere to give the thiolate
anion. This solution was added to a solution of the carbenoid
18 through a canula. Temperature of the reaction mixture
was gradually allowed to warm to 0 8C for 2 h. The reaction
was quenched by satd aq NH4Cl and the whole was
extracted with CHCl3. The organic layer was washed once
with water and dried over MgSO4. After removal of the
solvent, the product was purified by silica gel column
chromatography to give 20a (44.2 mg; 80%) as a colorless
oil; IR (neat) 2948, 2880, 1492, 1120, 1085, 1034, 908,
805 cmK1; 1H NMR d 1.71–1.76 (4H, m), 2.32 (3H, s), 2.40
(2H, t, JZ6.4 Hz), 2.53 (2H, t, JZ6.6 Hz), 3.98 (4H, s),
5.92 (1H, s), 7.10 (2H, d, JZ8.0 Hz), 7.21 (2H, d, JZ
8.3 Hz). MS m/z (%) 276 (MC, 100), 215 (12), 153 (63), 109
(27), 99 (17), 91 (17). Calcd for C16H20O2S: M, 276.1183.
Found: m/z 276.1179.
2.1.18. {(p-Tolylsulfanyl)methylene}cyclopentadecane
(20f). Colorless oil; IR (neat) 2928, 2857, 1492, 1459,
1216, 1092, 803, 759 cmK1; 1H NMR d 1.25–1.52 (24H, m),
2.16 (2H, t, JZ7.6 Hz), 2.27 (2H, t, JZ7.7 Hz), 2.31 (3H,
s), 5.90 (1H, s), 7.09 (2H, d, JZ7.9 Hz), 7.20 (2H, d, JZ
7.9 Hz). MS m/z (%) 344 (MC, 100), 124 (15), 95 (8), 69
(10), 55 (14). Calcd for C23H36S: M, 344.2535. Found: m/z
344.2529.
2.1.19. 2-Methylpropenyl p-tolyl sulfide (20g). Colorless
oil; IR (neat) 2967, 2910, 2727, 1892, 1492, 1440, 1372,
1
1302, 1171, 1091, 1062, 1017, 857, 804 cmK1; H NMR d
1.86, 1.87, 2.31 (each 3H, s), 5.88 (1H, s), 7.09, 7.20 (each
2H, d, JZ8.3 Hz). MS m/z (%) 178 (MC, 100), 163 (31),
135 (13), 105 (13), 91 (21). Calcd for C11H14S: M,
178.0815. Found: m/z 178.0806.
2.1.20. 2,2-Diphenylethenyl p-tolyl sulfide (20h). Color-
less needles; mp 84–85 8C, (AcOEt–hexane); IR (KBr)
3027, 1583, 1491, 1442, 816, 807, 775, 754, 701, 693 cmK1
;
1H NMR d 2.34 (3H, s), 6.82 (1H, s), 7.14–7.44 (14H, m).
Anal. Calcd for C21H18S: C, 83.40; H, 6.00; S, 10.60.
Found: C, 83.28; H, 5.96; S, 10.73%.
2.1.14. 8-{(4-Methoxyphenylsulfanyl)methylene}-1,4-
dioxaspiro[4.5]decane (20b). Colorless oil; IR (neat)
2949, 2883, 1593, 1494, 1287, 1245, 1120, 1084, 1033,
2.1.21. (Z)-2-Methyl-4-phenyl-1-(p-tolylsulfanyl)-1-
butene (20i). Colorless oil; IR (neat) 3026, 2922, 1604,
1493, 1454, 1376, 1091, 1032, 1017, 804, 743, 698 cmK1
;
1
908, 825, 757 cmK1; H NMR d 1.73 (4H, t, JZ6.5 Hz),
1H NMR d 1.86 (3H, d, JZ1.2 Hz), 2.31 (3H, s), 2.59 (2H,
dd, JZ8.3, 7.6 Hz), 2.76 (2H, dd, JZ8.6, 7.3 Hz), 5.91 (1H,
d, JZ1.2 Hz), 7.08 (2H, d, JZ8.0 Hz), 7.15–7.20 (3H, m),
7.23–7.24 (2H, m), 7.27–7.30 (2H, m). MS m/z (%) 268
(MC, 70), 177 (100), 149 (39), 144 (53), 129 (19), 91 (36).
Calcd for C18H20S: M, 268.1284. Found: m/z 268.1283.
2.37 (2H, t, JZ6.5 Hz), 2.52 (2H, t, JZ6.5 Hz), 3.79 (3H,
s), 3.98 (4H, s), 5.87 (1H, s), 6.85 (2H, d, JZ8.9 Hz), 7.29
(2H, d, JZ8.9 Hz). MS m/z (%) 292 (MC, 100), 231 (12),
153 (50), 139 (27), 109 (27). Calcd for C16H20O3S: M,
292.1132. Found: m/z 292.1138.
2.1.15. 8-{(4-Chlorophenylsulfanyl)methylene}-1,4-
dioxaspiro[4.5]decane (20c). Colorless needles; mp 50.5–
51.5 8C (hexane); IR (KBr) 2954, 2877, 1622, 1473, 1132,
2.1.22. (E)-2-Methyl-4-phenyl-1-(p-tolylsulfanyl)-1-
butene (20j). Colorless oil; IR (neat) 3026, 2921, 1601,
1493, 1454, 1376, 1091, 1030, 1017, 805, 745, 699 cmK1
;
1
1118, 1089, 1029, 913, 812, 682 cmK1; H NMR d 1.72
1H NMR d 1.88 (3H, s), 2.30 (3H, s), 2.47 (2H, t, JZ
7.8 Hz), 2.79 (2H, t, JZ7.8 Hz), 5.83 (1H, s), 7.05 (4H, s),
7.18–7.23 (3H, m), 7.29 (2H, t, JZ7.6 Hz). MS m/z (%) 268
(MC, 58), 177 (100), 149 (31), 144 (48), 129 (19), 91 (38).
Calcd for C18H20S: M, 268.1284. Found: m/z 268.1277.
(2H, t, JZ6.7 Hz), 1.76 (2H, t, JZ6.6 Hz), 2.43 (2H, t, JZ
6.6 Hz), 2.53 (2H, t, JZ6.6 Hz), 3.98 (4H, s), 5.91 (1H, s),
7.21 (2H, d, JZ8.6 Hz), 7.25 (2H, d, JZ8.6 Hz). Anal.
Calcd for C15H17ClO2S: C, 60.70; H, 5.77; Cl, 11.94; S,
10.80. Found: C, 60.82; H, 5.74; Cl, 11.87; S, 10.88%.
2.1.23. 8-(Deuterio-p-tolylsulfanylmethylene)-1,4-dioxa-
spiro[4.5]decane (26). Colorless oil; IR (neat) 2949, 2880,
1492, 1440, 1364, 1274, 1226, 1122, 1087, 1034, 929, 899,
2.1.16. 8-{(Dodecylsulfanyl)methylene}-1,4-dioxaspiro-
[4.5]decane (20d). Colorless oil; IR (neat) 2926, 2854,
1
1
1120, 1085, 1035, 908 cmK1; H NMR d 0.88 (3H, t, JZ
806 cmK1; H NMR d 1.73 (4H, quintet, JZ6.1 Hz), 2.31
7.0 Hz), 1.22–1.32 (16H, m), 1.36–1.39 (2H, m), 1.60 (2H,
t, JZ7.5 Hz), 1.68 (4H, t, JZ6.4 Hz), 2.30 (2H, t, JZ
6.4 Hz), 2.40 (2H, t, JZ6.6 Hz), 2.62 (2H, t, JZ7.3 Hz),
3.97 (4H, s), 5.66 (1H, s). MS m/z (%) 354 (MC, 81), 293
(16), 185 (77), 153 (100), 99 (34). Calcd for C21H38O2S: M,
354.2590. Found: m/z 354.2581.
(3H, s), 2.40 (2H, t, JZ6.4 Hz), 2.53 (2H, t, JZ6.6 Hz),
3.98 (4H, s), 7.10 (2H, d, JZ8.3 Hz), 7.21 (2H, d, JZ
8.3 Hz). MS m/z (%) 277 (MC, 100), 216 (14), 154 (60), 110
(27). Calcd for C16H19DO2S: M, 277.1245. Found: m/z
277.1242.
2.1.24. 2-(1,4-Dioxaspiro[4.5]dec-8-ylidene)-1-phenyl-2-
(p-tolylsulfanyl)ethanol (28a). To a solution of 17
(98.1 mg; 0.3 mmol) in 12 ml of dry toluene in a flame-
dried flask at K78 8C under argon atmosphere was added
2.1.17. 8-{(tert-Butylsulfanyl)methylene}-1,4-dioxaspiro-
[4.5]decane (20e). Colorless oil; IR (neat) 2955, 2881,
1457, 1364, 1270, 1120, 1085, 1035, 909 cmK1; 1H NMR d