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Helvetica Chimica Acta Vol. 87 (2004)
()-(2R)-1-{[(1R,6S)-2,2,6-Trimethylcyclohexyl]oxy}pentan-2-ol (3C (1'R,2R,6'S)). From 14 (1R,6S) and
(R)-10 in 18% yield; de 98%, ee 99% (Megadex). [a]2D0 26.3 (c 4.0, CHCl3). IR: 3426, 2923, 1454, 1380,
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1093. H-NMR: 3.8 (m, 1 H); 3.5 (m, 2H); 2.54 ( d, J 3.0, 1 H); 2.47 (d, J 10, 1 H); 1.3 1.7 (m, 10 H); 1.2
(m, 1 H); 0.97 (d, J 6.0, 3 H); 0.96 (s, 3 H); 0.93 (t, J 7.0, 3 H); 0.88 (s, 3 H). 13C-NMR: 92.4 (d); 78.3 (t); 70.7
(d); 40.1 (t); 36.8 (s); 35.3 (t); 34.9 (d t); 30.1 (q); 21.5 (t); 19.5 (q); 19.3 (q); 18.8 (t); 14.2( q). MS: 228 (100,
M ), 213 (3), 157 (33), 142 (19), 125 (44), 109 (31), 95 (16), 87 (20), 82 (53), 69 (56).
(À)-(2S)-1-{[(1S,6R)-2,2,6-Trimethylcyclohexyl]oxy}pentan-2-ol (3D (1'S,2S,6'R)). From 14 (1S,6R) and
(S)-10 in 25% yield. [a]2D0 À23.9 (c 4, CHCl3); de 98%, ee 99% (Megadex). Anal. data: identical to those
of 3C.
()-(2S)-1-{[(1R,3S,6S)-2,2,3,6-Tetramethylcyclohexyl]oxy}pentan-2-ol (4A (1'R,2S,3'S,6'S)). From 15
(1R,3S,6S) and (S)-10 in 41% yield; de 97% (1H-NMR), ee 99% (Megadex). [a]D20 25.5 (c 4.1, CHCl3).
IR: 3436, 2955, 1452, 1098. 1H-NMR: 3.80 (ddd, J 15.4, 7.5, 3.1, 1 H); 3.59 (dd, J 8.0, 3.1, 1 H); 3.40 (t, J 9.0,
1 H); 2.46 (d, J 3.5, 1 H); 2.42 (d, J 10.3, 1 H); 1.1 1.7 (m, 8 H); 1.0 (m, 2H); 0.98 ( s, 3 H); 0.95 (d, J 6.0,
3 H); 0.94 (t, J 7.1, 3 H); 0.82( d, J 6.3, 3 H); 0.75 (s, 3 H). 13C-NMR: 92.7 (d); 78.3 (t); 70.6 (d); 40.9 (d); 40.2
(s); 35.1 (d); 34.7 (d); 33.7 (t); 30.2( t); 26.2 (q); 15.6 (q); 18.8 (t); 15.6 (q); 14.1 (q); 13.6 (q). MS: 242 (60, M ),
157 (25), 138 (100), 123 (42), 109 (22).
(À)-(2R)-1-{[(1S,3R,6R)-2,2,3,6-Tetramethylcyclohexyl]oxy}pentan-2-ol (4B (1'S,2R,3'R,6'R)). From 15
(1S,3R,6R) and (R)-10 in 18% yield; de 96% (1H-NMR), ee 99% (Megadex). [a]D20 À26.2 (c 4.1, CHCl3).
Anal. data: identical to those of 4A.
()-(2R)-1-{[(1R,3S,6S)-2,2,3,6-Tetramethylcyclohexyl]oxy}pentan-2-ol (4C (1'R,2R,3'S,6'S)). From 15
(1R,3S,6S) and (R)-10 in 39% yield; de 96% (1H-NMR); ee 99% (Megadex). [a]D20 22.7 (c 3.9, CHCl3).
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IR: 3454, 2955, 1452, 1098. H-NMR: 3.80 (m, 1 H); 3.5 (m, 2H); 2.48 ( d, J 3.2, 1 H); 2.42 (d, J 9.9, 1 H);
1.1 1.7 (m, 8 H); 0.96 (d, J 6.0, 3 H); 0.95 (s, 3 H); 0.93 (t, J 7.1, 3 H); 0.9 1.0 (m, 2H); 0.82( d, J 6.0,
3 H); 0.73 (s, 3 H). 13C-NMR: 92.9 (d); 78.3 (t); 70.6 (d); 40.9 (d); 40.1 (s); 35.2( t); 34.7 (d); 33.8 (t); 30.2( t);
26.1 (q); 19.7 (q); 18.8 (t); 15.6 (q); 14.1 (q); 13.5 (q). MS: 242 (55, M ), 157 (25), 138 (100), 123 (42), 109 (21).
(À)-(2S)-1-{[(1S,3R,6R)-2,2,3,6-Tetramethylcyclohexyl]oxy}pentan-2-ol (4D (1'S,2S,3'R,6'R)). From 15
(1S,3R,6R) and (S)-10 in 35% yield; de 95% (1H-NMR), ee 99% (Megadex). [a]D20 À22.3 (c 4.5, CHCl3).
Anal. data: identical to those of 4C.
()-(2S)-1-[(2,2,6,6-Tetramethylcyclohexyl)oxy]butan-2-ol (16A (2S)). From 2,2,6,6-tetramethylcyclohex-
anol (17) with (S)-18 in 18% yield; ee 97% (Megadex). [a]2D0 5.4 (c 3.4, CHCl3). IR: 3420, 2930, 1460,
1380, 1097. 1H-NMR: 3.71 (m, 1 H); 3.61 (dd, J 8.7, 3.5, 1 H); 3.49 (dd, J 8.7, 7.5, 1 H); 2.64 (s, 1 H); 2.50
(d, J 3.5, 1 H); 1.25 1.60 (m, 6 H); 1.15 (dt, J 14, 4.0, 2H); 0.97 ( t, J 7.5, 3 H); 0.97 (s, 3 H); 0.96 (s, 3 H);
0.92( s, 3 H); 0.91 (s, 3 H). 13C-NMR: 92.7 (d); 78.5 (t); 72.4 (d); 40.2( t); 40.1 (t); 37.2( s); 37.1 (s); 32.6 (q); 32.5
(q); 26.0 (t); 21.0 (q); 20.9 (q); 18.5 (t); 10.0 (q). MS: 228 (3, M ), 138 (22), 123 (12), 109 (30), 82 (100), 69 (28),
55 (29), 41 (26).
(À)-(2R)-1-[(2,2,6,6-Tetramethylcyclohexyl)oxy]butan-2-ol (16B (2R)). From 17 with (R)-18 in 20% yield;
ee 97% (Megadex). [a]2D0 À5.4 (c 3.3, CHCl3). Anal. data: identical to those of 16A.
(Æ)-cis-1-{[2-(tert-Butyl)cyclohexyl]oxy}butan-2-ol ((Æ)-cis-19). From (Æ)-cis-21 with (Æ)-2-ethyloxirane
((Æ)-18) as a 60 :40 diastereoisomer mixture in 25% yield. 1H-NMR: major diastereoisomer: 3.77 (s, 1 H); 3.67
(m, 1 H); 3.36 (dd, J 8.7, 7.5, 1 H); 3.25 (dd, J 8.9, 3.2, 1 H); 2.38 (s, 1 H); 2.03 (d, J 13.9, 1 H); 1.77
(m, 1 H); 1.4 1.6 (m, 6 H); 1.0 1.3 (m, 3 H); 0.97 (t, J 7.5, 3 H); 0.91 (s, 9 H); minor diastereoisomer: 3.77
(s, 1 H); 3.67 (m, 1 H); 3.54 (dd, J 9.1, 3.5, 1 H); 3.08 (dd, J 9.1, 7.5, 1 H); 2.33 (s, 1 H); 2.03 (d, J 13.9,
1 H); 1.77 (m, 1 H); 1.4 1.6 (m, 6 H); 1.0 1.3 (m, 3 H); 0.98 (t, J 7.5, 3 H); 0.92( s, 9 H). 13C-NMR: major
diastereoisomer: 75.5 (d); 72.1 (d); 71.3 (t); 51.3 (d); 32.7 (s); 29.1 (t); 28.8 (q); 26.91 (t); 26.2 (t); 22.2 (t); 20.4
(t); 10.0 (q); minor diastereoisomer: 75.9 (d); 72.2 (d); 71.5 (t); 51.4 (d); 32.6 (s); 29.4 (t); 28.8 (q); 26.94 (t); 26.3
(t); 22.2 (t); 20.3 (t); 10.03 (q). MS: 228 (13, M ), 213 (10), 138 (27), 123 (12), 95 (13), 83 (50), 73 (39), 67 (32),
57 (100), 55 (40), 41 (45).
(À)-(2S)-1-{[(1R,2S)-2-(tert-Butyl)cyclohexyl]oxy}butan-2-ol (19A (1'R,2S,2'S)). From 21 (1R,2S) and
(S)-18 in 25% yield; ee > 99%, de 97% (Chirasil). [a]2D0 À57.6 (c 4.3, CHCl3). IR: 3442, 2932, 1449, 1365,
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1094. H-NMR: 3.65 (m, 1 H); 3.62( dd, J 9.5, 3.5, 1 H); 3.12( m, 2 H); 2 .2 7d(, J 3.5, 1 H); 2.12 (m, 1 H);
1.81 (dt, J 14, 3.0, 1 H); 1.70 (m, 3 H); 1.48 (quint., J 7.5, 2H); 1.24 ( ddd, J 12.5, 9.3, 3.5, 1 H); 1.16
(m, 3 H); 0.97 (t, J 7.5, 3 H); 0.96 (s, 9 H). 13C-NMR: 81.7 (d); 72.4 (d); 71.8 (t); 51.6 (d); 33.0 (s); 31.8 (t); 29.4
(q); 27.0 (t); 26.4 (t); 26.2 (t); 24.7 (t); 10.0 (q). MS: 228 (11, M ), 213 (10), 138 (27), 123 (15), 95 (16), 83 (58),
73 (46), 67 (38), 57 (100), 41 (53).
()-(2R)-1-{[(1S,2R)-(tert-Butyl)cyclohexyl]oxy}butan-2-ol (19B (1'S,2R,2'R)). From 21 (1S,2R) and (R)-
18 in 28% yield; ee > 99%, de 98%. [a]2D0 57.8 (c 4.6, CHCl3). Anal. data: identical to those of 19A.