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Y. Peng et al. / Tetrahedron 62 (2006) 1209–1215
2.1.1. 1-Vinyl-cycloheptanol (2a0). RfZ0.21 (PET/
AcOEtZ7:1); IR (film) nmax 3374, 3085, 2925, 2856,
1640, 1460, 1342, 1272, 1200, 1088, 1031, 995, 917,
(ESI) m/z obsd 189.1276 ([MCH]C, calcd 189.1274 for
C13H17O).
1
846 cmK1; H NMR (300 MHz, CDCl3) d 6.03 (dd, 1H,
2.1.7.
cis-1-Methylsulfanylmethyl-4-phenyl-cyclo-
JZ17.4, 10.8 Hz), 5.21 (d, 1H, JZ17.4 Hz), 4.99 (d, 1H,
JZ10.8 Hz), 1.80–1.37 (m, 12H) ppm; 13C NMR (50 MHz,
CDCl3) d 146.6, 110.1, 75.5, 41.1 (2C), 29.4 (2C), 22.1
(2C) ppm; HRMS (ESI) m/z obsd 141.1276 ([MCH]C,
calcd 141.1274 for C9H17O).
hexanol. (Compound 2d, cis/trans 3.9:1, total yield 26%),
RfZ0.04 (PET/AcOEtZ8:1); IR (film) nmax 3444, 3059,
3026, 2928, 2859, 1695, 1600, 1494, 1450, 1347, 1198,
1
1054, 972, 757, 699 cmK1; H NMR (80 MHz, CDCl3) d
7.33–7.18 (m, 5H), 2.92 (s, 2H), 2.63 (s, OH), 2.65–2.45 (m,
1H), 2.24 (s, 3H), 2.03–1.29 (m, 8H) ppm; 13C NMR
(50 MHz, CDCl3) d 146.0, 128.3, 126.7, 126.1, 71.4, 60.3,
43.7, 43.2, 37.5, 30.8, 21.0, 17.9, 14.1 ppm; EIMS (m/z, %):
236 (MC, 0.7), 218 (0.11), 174 (13), 157 (10), 129 (7), 91
(39), 77 (9), 62 (100); HRMS (ESI) m/z obsd 237.1311
([MCH]C, calcd 237.1308 for C14H21OS). trans-1-Methyl-
sulfanylmethyl-4-phenyl cyclohexanol (2d). RfZ0.043
(PET/AcOEtZ8:1); IR (film) nmax 3530, 3468, 3026,
2928, 2857, 1601, 1493, 1442, 1312, 1211, 1143, 1060,
2.1.2. 1-Oxa-spiro[2.5]octane. (Compound 1b, yield 50%),
RfZ0.69 (PET/AcOEtZ8:1); IR (film) nmax 2955, 2924,
1
2855, 1596, 1456, 1377, 1257, 1072, 1022, 802 cmK1; H
NMR (200 MHz, CDCl3) d 2.61 (s, 2H), 1.68–1.45 (m,
10H) ppm; HRMS (ESI) m/z obsd 113.0958 ([MCH]C,
calcd 113.0961 for C7H13O).
2.1.3. 1-Methylsulfanylmethyl-cyclohexanol. (Compound
2b, yield 30%), RfZ0.20 (PET/AcOEtZ7:1); IR (film) nmax
3446, 2930, 2856, 1446, 1349, 1242, 1171, 1147, 1058,
969 cmK1; 1H NMR (200 MHz, CDCl3) d 2.65 (s, 2H), 2.18
(s, 3H), 1.73–1.17 (m, 10H) ppm; EIMS (m/z, %): 160 (MC,
11), 142 (3), 99 (53), 81 (88), 62 (100); HRMS (ESI) m/z
obsd 161.0998 ([MCH]C, calcd 161.0995 for C8H17OS).
1
979, 756, 699 cmK1; H NMR (80 MHz, CDCl3) d 7.33–
7.21 (m, 5H), 2.69 (s, 2H), 2.52–2.40 (m, 1H), 2.23 (s, 3H),
2.06–1.45 (m, 8H) ppm; EIMS (m/z, %): 236 (MC, 8.3), 218
(1.8), 174 (81), 157 (6.1), 91 (100); HRMS (ESI) m/z obsd
237.1310 ([MCH]C, calcd 237.1308 for C14H21OS).
2.1.8. 2-Methyl-2-(4-methyl-pent-3-enyl)-oxirane. (Com-
pound 1e, yield 45%), RfZ0.91 (PET/AcOEtZ8:1); IR
(film) nmax 3035, 2966, 2923, 2857, 1449, 1384, 1265, 1108,
2.1.4. 6-Methyl-1-oxa-spiro[2.5]octane. (Compound 1c,
yield 40%), RfZ0.60 (PET/AcOEtZ8:1); IR (film) nmax
1
1
2922, 2852, 1597, 1447, 1261, 1024, 799 cmK1; H NMR
1072, 901, 796 cmK1; H NMR (200 MHz, CDCl3) d 5.09
(200 MHz, CDCl3) d 2.61 (d, JZ1.4 Hz, trans-OCH2), 2.56
(s, cis-OCH2), 1.90–1.66 (m, 4H), 1.55–0.80 (m, 5H), 0.94
(d, JZ6.2 Hz, cis-CH3), 0.92 (d, JZ6.6 Hz, trans-
CH3) ppm; 13C NMR (50 MHz, CDCl3) d 59.5, 54.8, 53.8,
33.9, 33.2, 32.6, 32.3, 31.4, 31.3, 22.0, 21.5 ppm; HRMS
(ESI) m/z obsd 127.1120 ([MCH]C, calcd 127.1118 for
C8H15O).
(t, 1H, JZ7.1 Hz), 2.59 (q, 2H, JZ6.4 Hz), 2.07 (q, 2H, JZ
7.6 Hz), 1.68 (s, 3H), 1.60 (s, 3H), 1.24–1.11 (m, 2H) ppm;
13C NMR (75 MHz, CDCl3) d 131.9, 123.6, 56.8, 53.9, 36.8,
25.6, 23.8, 20.9, 17.6 ppm; EIMS (m/z, %): 140 (MC, 0.04),
125 (0.2), 109 (6.5), 82 (7), 67 (32), 55 (19), 41 (100);
HRMS (ESI) m/z obsd 141.1277 ([MCH]C, calcd 141.1274
for C9H17O). 2,6-Dimethyl-1-methylsulfanyl-hept-5-en-2-ol
(2e, yield 21%). RfZ0.90 (PET/AcOEtZ8:1); IR (film)
nmax 3446, 2969, 2919, 2858, 1700, 1665, 1442, 1376, 1241,
2.1.5.
cis-4-Methyl-1-methylsulfanylmethyl-cyclo-
1
1150, 1114, 1021, 917, 835 cmK1; H NMR (200 MHz,
hexanol. (Compound 2c, cis/trans 10:1, total yield 15%),
RfZ0.1 (PET/AcOEtZ8:1); IR (film) nmax 3449, 2921,
CDCl3) d 5.11 (t, 1H, JZ6.8 Hz), 2.65 (d, 2H, JZ4.0 Hz),
2.26 (s, 1H, OH), 2.16 (s, 3H), 2.10–1.99 (m, 2H), 1.68
(s, 3H), 1.61 (s, 3H), 1.58–1.49 (m, 2H), 1.23 (s, 3H) ppm;
13C NMR (50 MHz, CDCl3) d 131.8, 124.1, 72.6, 47.7, 41.1,
26.1, 25.7, 22.7, 18.1, 17.6 ppm; EIMS (m/z, %): 188 (MC,
0.8), 173 (0.2), 170 (3.2), 155 (1), 26 (18), 109 (67), 69
(100); HRMS (ESI) m/z obsd 189.1310 ([MCH]C, calcd
189.1308 for C10H21OS).
1
2857, 1449, 1372, 1234, 998 cmK1; H NMR (200 MHz,
CDCl3) d 2.75 (s, 2H), 2.41 (s, 1H, OH), 2.18 (s, 3H), 1.80–
1.44 (m, 7H), 1.11–0.85 (m, 2H), 0.90 (d, 3H, JZ
6.4 Hz) ppm; 13C NMR (50 MHz, CDCl3) d 71.1, 44.3,
36.6, 31.4, 31.3, 21.1, 17.9 ppm; EIMS (m/z, %): 174 (MC,
9.3), 113 (49), 95 (89), 62 (100); HRMS (ESI) m/z obsd
175.1156 ([MCH]C, calcd 175.1152 for C9H19OS). trans-
4-Methyl-1-methylsulfanylmethyl-cyclohexanol (2c). RfZ
0.12 (PET/AcOEtZ8:1); IR (film) nmax 3445, 2923, 2859,
1453, 1089, 1049, 1009 cmK1; 1H NMR (200 MHz, CDCl3) d
2.59(s, 2H), 2.16 (s, 3H), 2.05 (s, 1H, OH), 1.71–1.29 (m, 9H),
0.91 (br s, 3H) ppm; EIMS (m/z, %): 174 (MC, 8.4), 113 (35),
95(64), 62(100);HRMS(ESI) m/zobsd175.1154([MCH]C,
calcd 175.1152 for C9H19OS).
2.1.9. 2-Methyl-4-phenyl-but-3-enal. (Compound 3f, yield
57%), RfZ0.51 (PET/AcOEtZ6:1); IR (film) nmax 3427,
2974, 2716, 1724, 1639, 1598, 1450, 968, 747, 694 cmK1; 1H
NMR(200 MHz,CDCl3)d9.66(d, 1H, JZ1.4 Hz), 7.41–7.25
(m, 5H), 6.55 (d, 1H, JZ16.0 Hz), 6.16 (dd, 1H, JZ16.0,
7.6 Hz), 3.26(t, 1H, JZ7.0 Hz), 1.33(d, 3H, JZ7.0 Hz) ppm;
EIMS(m/z, %):160(MC, 11),141(0.3), 131(100), 91(43), 77
(9.3); HRMS (ESI) m/z obsd 161.0963 ([MCH]C, calcd
161.0961 for C11H13O). 2-Methyl-1-methylsulfanyl-4-phenyl-
but-3-en-2-ol (2f, yield 25%). RfZ0.30 (PET/AcOEtZ6:1);
IR (film) nmax 3443, 3026, 2974, 2918, 1598, 1578, 1494,
1369, 1269, 1067, 970, 749, 694 cmK1; 1H NMR (200 MHz,
CDCl3) d 7.42–7.20 (m, 5H), 6.69 (d, 1H, JZ16.0 Hz), 6.25
(d, 1H, JZ16.0 Hz), 2.81 (q, 2H, JZ13.6 Hz) ppm; 13C NMR
(75 MHz, CDCl3) d 136.7, 135.1, 128.5, 128.0, 127.5, 126.4,
72.7, 48.2, 27.6, 18.0 ppm; EIMS (m/z, %): 208 (MC, 2), 147
2.1.6. 6-Phenyl-1-oxa-spiro[2.5]octane. (Compound 1d,
yield 48%), RfZ0.23 (PET/AcOEtZ8:1); IR (film) nmax
3025, 2998, 2935, 2856, 1601, 1491, 1446, 1181, 1097, 979,
1
911, 753, 699 cmK1; H NMR (80 MHz, CDCl3) d 7.35–
7.25 (m, 5H), 2.70 (s, 2H), 2.60–2.53 (m, 1H), 2.13–1.38
(m, 8H) ppm; 13C NMR (50 MHz, CDCl3) d 146.1, 128.4,
126.8, 126.7, 126.2, 126.1, 59.1, 54.9, 53.9, 43.3, 33.8, 33.2,
31.5 ppm; EIMS (m/z, %): 188 (MC, 13), 174 (4), 168 (4.8),
143 (12), 129 (19), 115 (30), 104 (100), 91 (59); HRMS