M. Kimura et al. / Tetrahedron 61 (2005) 3709–3718
3717
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2.46 (dd, JZ14.1, 7.4 Hz, 1H), 3.52 (ddd, JZ10.5, 4.0,
1.9 Hz, 1H), 5.13 (d, JZ10.0 Hz, 1H), 5.14 (d, JZ16.8 Hz,
1H), 5.86 (dddd, JZ16.8, 10.0, 8.5, 5.9 Hz, 1H), 6.30 (dt,
JZ15.9, 7.3 Hz, 1H), 6,41 (d, JZ15.9 Hz, 1H), 7.18–7.36
(m, 5H); 13C NMR (100 MHz, CDCl3): dZ21.4, 21.5, 26.2,
30.9, 31.4, 35.8, 36.0, 40.5, 75.4, 117.6, 125.9, 126.8, 127.5,
128.3, 131.8, 136.6, 137.7; HRMS calcd C19H26O
270.1984, found m/z (relative intensity): 270.1978 (MC,
100), 269 (2), 268 (7).
964, 740, 694 cmK1; H NMR (300 MHz, CDCl3): d 0.92
(d, JZ6.6 Hz, 6H, Z-isomer), 0.93 (d, JZ6.6 Hz, 6H,
Z-isomer), 0.98 (d, JZ6.6 Hz, 6H, E-isomer), 0.99 (d, JZ
6.6 Hz, 6H, E-isomer), 1.43 (d, JZ6.6 Hz, 4H), 1.85 (sept,
JZ6.6 Hz, 2H, E-isomer), 2.42 (d, JZ7.4 Hz, 2H,
E-isomer), 2.56 (dd, JZ7.4, 1.9 Hz, 2H, Z-isomer), 5.74
(dt, JZ11.5, 7.4 Hz, 1H, Z-isomer), 6.23 (dt, JZ15.9,
7.4 Hz, 1H, E-isomer), 6.45 (d, JZ15.7 Hz, E-isomer), 6.56
(d, JZ11.5 Hz, 1H, Z-isomer); 13C NMR (100 MHz,
CDCl3): d 23.9, 24.8, 24.9, 44.1, 48.6, 75.6, 125.8, 125.9,
127.0, 128.4, 133.4, 137.3; HRMS calcd for C18H28O
260.2140, found m/z (relative intensity): 260.2087 (MC, 1),
245 (1), 243 (4), 204 (16), 203 (100).
4.2.5. Cyclohexyl (2-methylenecyclohexyl)methanol (3o).
IR (neat) 3489, 3069, 2852, 2795, 1643, 1448, 1390, 1259,
1
1085, 980, 893, 866, 682, 642 cmK1; H NMR (300 MHz,
CDCl3): d 1.19–1.78 (m, 18H), 2.17–2.29 (m, 3H), 3.60 (d,
JZ9.9 Hz, 1H), 4.77 (s, 1H), 4.85 (s, 1H); 13C NMR
(100 MHz, CDCl3): d 22.3, 24.2, 26.4, 26.6, 27.0, 28.1,
28.8, 31.2, 32.7, 38.9, 46.5, 72.5, 109.9, 150.1; HRMS calcd
C14H24O 208.1827, found m/z (relative intensity): 208.1788
(MC, 20), 207 (11), 206 (53), 191 (61), 190 (100).
4.2.9. Mixture of 4-Isobutyl-3,6-dimethyl-1-hepten-4-ol
(g-7e) and (E)-4-isobutyl-2-methyl-6-octen-4-ol (a-7e).
IR (neat) 3495, 3070, 2951, 2933, 2859, 1729, 1640, 1469,
1261, 1108, 914, 804, 722, 668 cmK1; 1H NMR (400 MHz,
CDCl3): d 0.79 (d, JZ6.3 Hz, 3H, a-isomer), 0.80 (d, JZ
6.3 Hz, 3H, a-isomer), 0.81 (d, JZ6.3 Hz, 3H, a-isomer),
0.82 (d, JZ6.3 Hz, 3H, a-isomer), 0.83 (d, JZ6.3 Hz, 3H,
a-isomer), 0.88 (d, JZ6.8 Hz, 3H), 0.89 (d, JZ6.8 Hz, 3H),
0.90 (d, JZ6.8 Hz, 3H), 0.91 (d, JZ6.8, 3H), 0.92 (d, JZ
6.8 Hz, 3H), 1.20 (s, 1H), 1.21 (dd JZ14.4, 6.8 Hz, 1H),
1.29 (dd JZ14.4, 6.8 Hz, 1H), 1.30 (dd JZ14.4, 6.8 Hz,
1H), 1.37 (dd JZ14.4, 6.8 Hz, 1H), 1.56–1.65 (m, 2H,
a-isomer), 1.75 (sept, JZ6.8 Hz, 1H), 1.76 (sept, JZ
6.8 Hz, 1H), 2.15–2.23 (m, 2H, a-isomer), 2.36 (dq, JZ8.3,
6.8 Hz, 1H), 5.01 (dd, JZ10.5, 1.9 Hz, 1H), 5.02 (dt, JZ
17.1, 1.9 Hz, 1H), 5.31–5.40 (m, 1H, a-isomer), 5.55 (dt,
JZ17.3 Hz, 1H), 5.76 (ddd, JZ17.1, 10.5, 1.9 Hz, 1H); 13C
NMR (100 MHz, CDCl3): d 13.9, 22.5, 22.6, 23.5, 23.6,
23.7, 24.1, 44.1, 44.2, 45.0, 75.5, 115.2, 139.5; HRMS calcd
for MCKMe2 C11H21O 169.1590, found m/z (relative
intensity): 169.1590 (MCKMe2, 5), 167 (4), 143 (100), 141
(8).
4.2.6. Mixture of 2,2-dimethyl-4-phenyl-5-hexen-3-ol (3t)
and (E)-2,2-dimethyl-6-phenyl-5-hexen-3-ol (3u). IR
(neat) 3456, 3024, 2955, 2869, 2361, 1597, 1474, 1366,
1
1180, 1072, 1011, 972, 918, 741, 694 cmK1; H NMR (3t,
300 MHz, CDCl3): d 0.93 (s, 9H, anti-isomer), 0.97 (s, 9H,
syn-isomer), 1.45 (d, JZ4.1 Hz, 1H, syn–isomer), 1.75 (d,
JZ4.6 Hz, 1H, anti-isomer), 3.53–3.66 (m, 2H, antiCsyn-
isomers), 5.03 (d, JZ10.2 Hz, 1H, syn-isomer), 5.06 (d, JZ
17.6 Hz, 1H, syn-isomer), 5.12 (d, JZ17.6 Hz, 1H, anti-
isomer), 5.18 (d, JZ10.3 Hz, 1H, anti-isomer), 6.16 (ddd,
JZ17.6, 10.2, 8.2 Hz, 1H, syn-isomer), 6.31 (ddd, JZ17.6,
10.3, 8.2 1H, anti-isomer), 7.18–7.39 (m, 5H, antiCsyn-
isomers); 13C NMR (3t, 100 MHz, CDCl3): d 26.6 (anti-
isomer), 26.7 (syn-isomer), 35.6 (anti-isomer), 35.8 (syn-
isomer), 52.7 (anti-isomer), 53.7 (syn-isomer), 81.3 (syn-
isomer), 81.4 (anti-isomer), 114.6 (syn-isomer), 117.0 (anti-
isomer), 126.1 (anti-isomer), 126.5 (syn-isomer), 127.7
(anti-isomer), 128.2 (syn-isomer), 128.3 (anti-isomer),
128.7 (syn-isomer), 138.6 (antiCsyn-isomers), 141.3 (syn-
isomer), 144.2 (anti-isomer); 1H NMR (3u, 300 MHz,
CDCl3): d 1.00 (s, 9H), 1.67 (s, 1H), 2.21 (dddd, JZ14.2,
10.5, 8.3, 1.4 Hz, 1H), 2.55 (ddt, JZ14.2, 6.1, 1.4 1H), 3.38
(d, JZ10.5 Hz, 1H), 6.31 (ddd, JZ15.9, 8.3, 6.1 1H), 6.53
(d, JZ15.9 Hz, 1H), 7.23–7.41 (m, 5H); 13C NMR (3u,
100 MHz, CDCl3): d 25.8, 34.7, 35.7, 78.6, 125.9, 127.0,
127.9, 128.4, 132.6, 137.1; HRMS calcd C14H20O
204.1514, found m/z (relative intensity): 204.1516 (MC,
26), 129 (6), 119 (36), 118 (100), 117 (43).
4.2.10. (E)-2-Methyl-3,6-diphenylhex-5-en-3-ol (a-7i). IR
(neat) 3560, 3487, 3058, 3026, 2964, 2875, 2795, 1598, 1495,
1447, 1384, 1238, 1173, 1003, 970, 891, 764, 746, 702 cmK1
;
1H NMR (300 MHz, CDCl3): d 0.79 (d, JZ6.8 Hz, 3H),
0.97 (d, JZ6.8 Hz, 3H), 1.95 (s, 1H), 2.07 (sept, JZ6.8 Hz,
1H), 2.70 (dd, JZ14.0, 9.3 Hz, 1H), 2.93 (ddd, JZ14.0, 5.6,
1.7 Hz, 1H), 5.86 (ddd, JZ15.6, 9.3, 5.6 Hz, 1H), 6.46 (d,
JZ15.6 Hz, 1H), 7.15–7.41 (m, 10H); 13C NMR (100 MHz,
CDCl3): d 16.8, 17.6, 37.8, 43.2, 78.2, 125.2, 125.9, 126.0,
126.3, 127.2, 127.9, 128.3, 134.3, 136.9, 144.9; HRMS
calcd for C19H22O 266.1671, found m/z (relative intensity):
266.1646 (MC, 19), 251 (3), 248 (3), 224 (19), 223 (100).
4.2.7. 4-Isobutyl-6-methylhept-1-en-4-ol (7c). IR (neat)
3485, 3076, 2954, 2927, 2869, 1709, 1639, 1468, 1367,
4.2.11. (E)-1,1,4-Triphenyl-3-buten-1-ol (a-7l). IR (KBr)
3541, 3456, 3021, 2839, 1596, 1488, 1357, 1203, 1057, 972,
910, 748, 694 cmK1; 1H NMR (300 MHz, CDCl3): d 2.60 (s,
1H), 3.21 (d, JZ7.4 Hz, 2H), 6.04 (dt, JZ15.9, 7.4 Hz, 1H),
6.56 (d, JZ15.9 Hz, 1H), 7.20–7.49 (m, 15H); 13C NMR
(100 MHz, CDCl3): d 46.1, 77.4, 124.5, 126.0, 126.2, 126.9,
127.5, 128.2, 128.4, 135.3, 136.8, 146.4; HRMS calcd for
C22H20O 300.1514, found m/z (relative intensity): 300.1498
(MC, 10), 283 (85), 282 (100).
1261, 1097, 1018, 914, 866, 804, 661 cmK1 1H NMR
;
(300 MHz, CDCl3): d 0.90 (d, JZ6.6, 6H), 0.91 (d, JZ6.6,
6H), 1.23 (s, 1H), 1.36 (d, JZ6.6, 4H), 1.75 (sept, JZ6.6,
2H), 2.21 (d, JZ7.4, 2H), 5.05 (d, JZ17.2 Hz, 1H), 5.07 (d,
JZ10.4 Hz, 1H), 5.77 (ddt, JZ17.2, 10.4, 7.4 Hz, 1H); 13C
NMR (100 MHz, CDCl3): d 23.9, 24.7. 24.8, 44.8, 48.4,
75.1, 118.5, 134.2; HRMS calcd C12H24O 184.1827, found
m/z (relative intensity): 184.1792 (MC, 4), 169 (3), 157
(18), 143 (100).
4.2.12. 2-Methyl-1,1-diphenyl-3-buten-1-ol (g-7m). IR
(neat) 3514, 3058, 2977, 1598, 1578, 1493, 1448, 1319,
1278, 1153, 1001, 941, 810, 766, 748, 702 cmK1; 1H NMR
4.2.8. 4-Isobutyl-6-methyl-1-phenylhept-1-en-4-ol
(a-7d). IR (neat) 3487, 3024, 2955, 2360, 1466, 1366,