S. Panev, V. Dimitrov / Tetrahedron: Asymmetry 11 (2000) 1517±1526
1523
C, 79.18; H, 13.29. Found: C, 78.04; H, 12.79. MS (EI) m/z (rel. int.): 212 (M+Á, 5), 155 (52), 137
1
(15), 127 (100), 95 (14), 81 (29), 69 (12), 57 (12), 55 (12), 43 (C2H3O, 16). H NMR (CDCl3, 300
K): ꢁ=0.82 (qd, 1H, H-4ax, J=12.2, 4.4 Hz), 0.87 (d, 3H, H-10, J=5.9 Hz), 0.89 (d, 3H, H-9,
J=6.6 Hz), 0.89 (d, 3H, H-8, J=6.6 Hz), 0.91 (t, 3H, H-14), 1.07 (t, 1H, H-6ax, J=12.5 Hz), 1.10
(dm, 1H, H-2), 1.15±1.30 (m, 2H, H-12), 1.20±1.38 (m, 2H, H-13), 1.41 (qd, 1H, H-3ax, J=12.5,
3.4 Hz), 1.43±1.56 (m, 1H, H-3eq), 1.47 (dm, 1H, H-6eq), 1.38±1.50 (m, 1H, H-11), 1.57±1.70
(m, 1H, H-11), 1.59±1.75 (m, 1H, H-5), 1.75 (dm, 1H, H-4eq), 2.08 (quintd, 1H, H-7, J=6.9, 1.7
Hz).
3.7. (1S,2S,5R)-1-t-Butyl-2-isopropyl-5-methyl-cyclohexan-1-ol 16a
Without CeCl3. Following the general procedure, from 0.31 g (2.01 mmol) 1 in 4 ml THF and
3.4 ml of a 0.94 M t-BuLi solution in pentane (3.20 mmol) were obtained after column chroma-
tography (1 13 mm, h=430 mm, 26 g silica gel, petroleum ether:Et2O=10:1) 0.20 g (47%) 16a
and 0.06 g mixed fraction of 1 and 16a (48:52 by NMR). The conversion of 1 was 56%.
With CeCl3. Following the general procedure, from 0.30 g (1.94 mmol) 1, 0.52 g (2.11 mmol)
CeCl3 in 7 ml THF and 3.3 ml of a 0.94 M t-BuLi solution in pentane (3.10 mmol) were obtained
after column chromatography (1 17 mm, h=490 mm, 41 g silica gel, petroleum ether:Et2O=5:1)
20
D
0.33 g (80%) 16a (colorless oil). ꢀ ^0.6 (c=1.13, CHCl3). Anal. calcd for C14H28O (212.38): C,
79.18; H, 13.29. Found: C, 78.90; H, 12.83. MS (EI) m/z (rel. int.): 212 (M+Á, 0.2), 155 (47), 137
(31), 127 (57), 109 (16), 95 (51), 85 (15), 81 (88), 69 (35), 57 (53), 55 (29), 43 (C2H3O, 100), 41 (46).
1H NMR (CDCl3, 300 K): ꢁ=0.79 (qd, 1H, H-4ax, J=11.9, 4.3 Hz), 0.87 (d, 3H, H-10, J=6.1
Hz), 0.88 (d, 3H, H-9, J=6.9 Hz), 0.89 (d, 3H, H-8, J=6.6 Hz), 0.94 (dd, 1H, H-6ax, J=14.4, 13.2
Hz), 1.02 (s, 9H, 3Me), 1.18 (s, 1H, OH), 1.28 (ddd, 1H, H-2, J=11.3, 3.6, 2.0 Hz), 1.42 (qd, 1H,
H-3ax, J=12.2, 3.2 Hz), 1.47±1.54 (m, 1H, H-3eq), 1.58±1.70 (m, 1H, H-5), 1.62 (dm, 1H, H-6eq,
J=12.2 Hz), 1.73 (dm, 1H, H-4eq, J=12.0 Hz), 2.41 (quintd, 1H, H-7, J=6.9, 2.0 Hz).
3.8. (1S,2S,5R)-1-Phenyl-2-isopropyl-5-methyl-cyclohexan-1-ol 17a and (1R,2S,5R)-1-phenyl-2-
isopropyl-5-methyl-cyclohexan-1-ol 17b
Without CeCl3. Following the general procedure, from 0.30 g (1.94 mmol) 1 in 4 ml THF and
2.4 ml of a 1.06 M PhMgBr solution in Et2O (2.54 mmol) were obtained after column chroma-
tography (1 17 mm, h=490 mm, 43 g silica gel, petroleum ether:Et2O=10:1) 0.34 g mixed
fraction of 1 and 17a (13:87 by NMR) and 0.01 g of 17b (2%). The yield of 17 was 71% (extra-
polated by means of NMR).
With CeCl3. Following the general procedure, from 0.14 g (0.91 mmol) 1, 0.23 g (0.93 mmol)
CeCl3 in 7 ml THF and 1.2 ml of a 1.06 M PhMgBr solution in Et2O (1.27 mmol) were obtained after
column chromatography (1 13 mm, h=460 mm, 15 g silica gel, petroleum ether:Et2O=10:1)
0.16 g (76%) 17a (colorless oil) and 0.01 g of 17b (5%).
20
Data of 17a. ꢀ ^5.4 (c 1.05, CHCl3). Anal. calcd for C16H24O (232.37): C, 82.70; H, 10.41.
D
Found: C, 82.35; H, 10.49. MS (EI) m/z (rel. int.): 232 (M+Á, 19), 147 (100), 133 (4), 120 (12), 105
(21), 91 (6), 77 (14), 69 (12), 55 (11), 43 (C2H3O, 5), 41 (13). 1H NMR (CDCl3, 300 K): ꢁ=0.73 (d,
3H, H-9, J=7.1 Hz), 0.83 (d, 3H, H-8, J=6.9 Hz), 0.90 (d, 3H, H-10, J=6.4 Hz), 1.07 (dm, 1H,
H-4ax), 1.44 (dd, 1H, H-6ax, J=12.9, 12.0 Hz), 1.50 (quintd, 1H, H-7), 1.58±1.68 (m, 3H, H-2, H-
3ax, H-3eq), 1.63 (dm, 1H, H-6eq), 1.80±1.90 (m, 1H, H-5), 1.88 (dm, 1H, H-4eq, J=12.5 Hz), 7.22
(tt, 1H, H-14, J=7.1, 1.6 Hz), 7.34 (td, 2H, H-13, J=7.6, 0.8 Hz), 7.46 (d, 2H, H-12, J=7.6 Hz).