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Helvetica Chimica Acta – Vol. 92 (2009)
1460, 1374, 1360, 1304, 1269, 1221, 1195, 1169, 1134, 1115, 1083, 1057, 1013, 970, 920, 840, 801, 698.
1H-NMR: major: 0.77 (s, 3 H); 0.96 (d, J ¼ 7, 3 H); 1.10 (s, 3 H); 1.52 (br. s, 1 OH); 1.59 (s, 3 H); 1.8 – 2.0
(m, 2 H); 2.12 – 2.22 (m, 2 H); 2.25 – 2.38 (m, 1 H); 2.51 – 2.6 (m, 1 H); 4.9 (s, 1 H); 5.27 (s, 1 H); minor:
0.77 (s, 3 H); 0.88 (d, J ¼ 7, 3 H); 1.11 (s, 3 H); 1.47 (br. s, 1 OH); 1.59 (s, 3 H); 1.8 – 2.0 (m, 2 H); 2.12 –
2.22 (m, 2 H); 2.25 – 2.38 (m, 1 H); 2.51 – 2.6 (m, 1 H); 4.92 (s, 1 H); 5.27 (s, 1 H). 13C-NMR: major: 148.6
(s); 147.4 (s); 121.6 (d); 111.7 (d); 55.4 (d); 47.8 (s); 41.8 (t); 34.1 (t); 34.0 (d); 27.0 (q); 21.0 (q); 17.3 (q);
12.8 (q); minor: 147.8 (s); 147.4 (s); 121.6 (d); 111.4 (d); 55.1 (d); 47.7 (s); 41.3 (t); 34.3 (t); 34.0 (d); 27.0
.
(q); 21.0 (q); 16.3 (q); 12.8 (q). MS: major: 211 (100, Mþ ), 196 (61), 178 (20), 150 (31), 136 (93), 120
.
(35), 108 (63), 93 (42), 79 (31), 67 (19), 55 (20), 41 (32); minor: 211 (100, Mþ ), 196 (62), 178 (18), 150
(28), 136 (88), 120 (35), 108 (60), 93 (38), 79 (30), 67 (16), 55 (20), 41 (30).
(ꢀ)-2-Methyl-4-[(1R)-2,2,3-trimethylcyclopent-3-en-1-yl](1,1,4,4-2H4)pent-4-en-1-ol ((ꢀ)-19b). Ob-
tained in 88% yield from (ꢀ)-18b and 0.5 mol-equiv. of LiAlD4, as described for (ꢀ)-17a. a2D0 ¼ ꢀ60.7
(neat, l ¼ 1 dm). B.p. 1308/0.3 mbar. IR: 3340, 3037, 2955, 2925, 2868, 2313, 2189, 2081, 1656, 1595, 1459,
1374, 1360, 1331, 1306, 1274, 1221, 1134, 1116, 1085, 1056, 1012, 970, 919, 799, 758, 721, 693, 650, 609.
1H-NMR: major: 0.77 (s, 3 H); 0.96 (d, J ¼ 7, 3 H); 1.10 (s, 3 H); 1.45 (br. s, OH); 1.59 (s, 3 H); 1.8 – 2.0
(m, 2 H); 2.12 – 2.22 (m, 2 H); 2.25 – 2.38 (m, 1 H); 2.51 – 2.6 (m, 1 H); 5.27 (s, 1 H); minor: 0.77 (s, 3 H);
0.88 (d, J ¼ 7, 3 H); 1.11 (s, 3 H); 1.39 (br. s, 1 OH); 1.59 (s, 3 H); 1.8 – 2.0 (m, 2 H); 2.12 – 2.22 (m, 2 H);
2.25 – 2.38 (m, 1 H); 2.51 – 2.6 (m, 1 H); 5.27 (s, 1 H). 13C-NMR: major: 148.5 (s); 147.4 (s); 121.6 (d);
55.5 (d); 47.8 (s); 41.8 (t); 34.1 (t); 34.0 (d); 27.0 (q); 21.0 (q); 17.3 (q); 12.8 (q); minor: 147.8 (s); 147.4 (s);
121.6 (d); 55.1 (d); 47.7 (s); 41.2 (t); 34.2 (t); 34.0 (d); 27.0 (q); 21.0 (q); 16.3 (q); 12.8 (q). MS: major: 212
.
(100, Mþ ), 197 (59), 179 (17), 151 (28), 137 (99), 123 (31), 121 (39), 109 (52), 107 (58), 93 (50), 79 (30),
.
67 (20), 55 (20), 41 (28); minor: 212 (100, Mþ ), 197 (59), 179 (17), 151 (28), 137 (90), 123 (30), 121 (39),
109 (50), 107 (55), 95 (38), 93 (48), 79 (28), 67 (20), 55 (20), 41 (28).
(ꢀ)-2-[(1R)-2,2,3-Trimethylcyclopent-3-en-1-yl](1,3-2H2)propanal ((ꢀ)-20). Obtained in 70%
yield16) from (ꢀ)-16d and 0.5 mol-equiv. of LiAlD4, as described for (ꢀ)-17a. a2D0 ¼ ꢀ8.03 (neat, l ¼
1 dm). B.p. 1008/0.3 mbar. IR: 3038, 2957, 2933, 2869, 2183, 2047, 1715, 1647, 1560, 1463, 1436, 1385,
1
1375, 1362, 1299, 1214, 1177, 1118, 1016, 968, 903, 846, 799, 753. H-NMR: major: 0.93 (s, 3 H); 1.11 (s,
3 H); 1.15 (dt, J ¼ 1, 7, 2 H); 1.59 (s, 3 H); 1.92 – 2.0 (m, 1 H); 2.0 – 2.18 (m, 1 H); 2.24 – 2.36 (m, 1 H);
2.48 – 2.56 (m, 1 H); 5.22 (s, 1 H); minor: 0.86 (s, 3 H); 0.99 (s, 3 H); 1.07 (dt, J ¼ 1, 7, 2 H); 1.59 (s, 3 H);
1.92 – 2.0 (m, 1 H); 2.0 – 2.18 (m, 1 H); 2.24 – 2.36 (m, 1 H); 2.48 – 2.56 (m, 1 H); 5.25 (s, 1 H). 13C-NMR:
major: 148.4 (s); 121.4 (d); 51.8 (d); 47.9 (d); 47.6 (s); 33.5 (t); 27.1 (q); 19.9 (q); 13.2 (t); 12.4 (q); minor:
148.6 (s); 121.1 (d); 50.8 (d); 47.9 (d); 46.9 (s); 33.4 (t); 26.4 (q); 20.3 (q); 13.1 (t); 12.5 (q). MS: major:
.
.
168 (1, Mþ ), 125 (16), 108 (100), 93 (40), 82 (11), 77 (8), 67 (6), 55 (5), 41 (8); minor: 168 (1, Mþ ), 125
(8), 108 (100), 93 (65), 82 (7), 77 (7), 67 (6), 55 (5), 41 (8).
(þ)-2-{(1S)-1-[(1R)-3,3-Dimethylcyclohexyl]ethoxy}-2-methylpropyl (3,3,3-2H3)Propanoate ((þ)-
22a). (D3)Propanoic acid (1.00 g, 13 mmol) was added to a soln. of alcohol (þ)-21a (2.96 g, 13 mmol),
DCC (2.68 g, 13 mmol), and DMAP (29.6 mg, 0.243 mmol) in CH2Cl2 (50 ml). After 24 h, Et2O (50 ml)
was added, and the mixture was filtered through Celiteꢀ, the filtrate dried (Na2SO4) and concentrated,
and the residue bulb-to-bulb distilled: (þ)-22a (55%). a2D0 ¼ þ7.3 (neat, l ¼ 1 dm). B.p. 908/0.32 mbar. IR:
2972, 2924, 2863, 2232, 2128, 2085, 1740, 1462, 1425, 1385, 1365, 1343, 1268, 1160, 1118, 1042, 978, 952, 927,
902, 849, 820, 756, 694. 1H-NMR: 0.8 – 0.9 (m, 2 H); 0.88 (s, 3 H); 0.90 (s, 3 H); 1.05 – 1.08 (m, 1 H); 1.07
(d, J ¼ 7, 3 H); 1.19 (s, 6 H); 1.3 – 1.39 (m, 2 H); 1.4 – 1.48 (m, 2 H); 1.52 – 1.59 (m, 1 H); 1.63 – 1.7 (m,
1 H); 2.35 (s, 2 H); 3.35 – 3.38 (m, 1 H); 3.95 (s, 2 H). 13C-NMR: 174.3 (s); 73.7 (s); 71.8 (d); 70.3 (t); 42.3
(t); 40.4 (d); 39.4 (t); 33.7 (q); 30.7 (s); 28.4 (t); 27.5 (t); 24.7 (q); 24.1 (q); 23.8 (q); 22.3 (t); 19.7 (q). MS:
.
287 (0, Mþ ), 212 (1), 197 (5), 139 (44), 132 (100), 123 (8), 97 (7), 83 (25), 69 (15), 60 (45), 55 (11).
(þ)-2-{(1S)-1-[(1R)-3,3-Dimethylcyclohexyl]ethoxy}-2-oxoethyl (3,3,3-2H3)Propanoate ((þ)-22b).
Obtained in 93% yield as described for (þ)-22a. a2D0 ¼ þ11.5 (neat, l ¼ 1 dm). B.p. 1208/0.32 mbar. IR:
2928, 2862, 2234, 2118, 1746, 1452, 1422, 1385, 1364, 1282, 1218, 1157, 1102, 1069, 1054, 1031, 1010, 971,
948, 891, 845, 790, 728, 695, 623. 1H-NMR: 0.82 – 0.86 (m, 2 H); 0.88 (s, 3 H); 0.91 (s, 3 H); 1.0 – 1.1 (m,
1 H); 1.19 (d, J ¼ 7, 3 H); 1.30 – 1.46 (m, 2 H); 1.55 – 1.70 (m, 2 H); 1.75 – 1.95 (m, 2 H); 2.45 (s, 2 H); 4.60
(s, 2 H); 4.78 (quint., J ¼ 7, 1 H ) . 13C-NMR: 173.8 (s); 167.6 (s); 76.3 (d); 60.8 (t); 41.1 (t); 39.1 (t); 38.3
.
(d); 33.5 (q); 30.5 (s); 28.3 (t); 27.0 (t); 24.6 (q); 21.9 (t); 17.0 (q). MS: 273 (0, Mþ ), 258 (1), 138 (51), 123
(100), 118 (61), 109 (59), 95 (50), 90 (28), 83 (57), 81 (33), 69 (68), 60 (76), 55 (39), 41 (30).