Helvetica Chimica Acta Vol. 87 (2004)
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MS (selected isomer): 322 (peak, M ), 200 (38), 173 (22), 134 (27), 133 (100), 107 (26), 106 (16), 105 (85), 91
(17), 79 (12), 77 (31), 67 (32).
A soln. of the benzoate mixture (82 mg) and 50% NaOH (25 mg, 0.625 mmol) in MeOH (3 ml) was
refluxed for 2 h. MeOH was evaporated, H2O (200 ml) added, and the aq. layer extracted with CH2Cl2. The org.
layer was washed with H2O and evaporated: (E/Z)-ent-10b 80 :20 (52 mg, 52%, over two steps). 1H-NMR: (E)-
ent-10b: 0.97 (d, J 6.8, MeÀC(3)); 1.03 1.14 (m, HaÀC(10')); 1.12 (d, J 6.4, MeC(1)); 1.40 (dddd, J 8.4,
2.8, 1.5, 1.5, HbÀC(10')); 1.80 1.90 (m, HaÀC(9')); 1.86 1.98 (m, HaÀC(3')); 2.00 2.13 (m, HÀC(1'),
HbÀC(9')); 2.03 2.22 (HÀC(2')); 2.23 (ddq, J 9.7, 6.6, 6.6, HÀC(3)); 2.39 (br. s, HÀC(7')); 2.60
(ddddd, J 17.2, 9.7, 2.2, 2.2, 1.5, HbÀC(3')); 2.64 2.72 (m, HÀC(6')); 3.58 (dq, J 6.2, 6.2, HÀC(2)); 5.09
(dt, J 9.9, 2.2, HÀC(4)); 5.47 (dddd, J 5.6, 2.4, 2.4, 2.4, HÀC(5')); 5.68 (dddd, 5.7, 2.0, 2.0, 2.0, HÀC(4'));
(Z)-ent-10b: 0.99 (d, J 6.8, H3CÀC(3)); 1.16 (d, J 6.2, Me(1)); 3.59 (dq, J 6.2, 6.2, HÀC(2)); 4.86 (d, J
9.5, HÀC(4)). 13C-NMR: (E)-ent-10b: 16.6 (q, MeÀC(3)); 20.2 (q, C(1)); 32.3 (t, C(10')); 35.7 (t, C(9')); 39.7
(t, C(3')); 40.8 (d, C(3)); 43.1 (d, C(2')); 43.2 (d, C(1')); 49.3 (d, C(7')); 55.9 (d, C(6')); 72.1 (d, C(2)); 119.1
(d, C(4)); 131.5 (d, C(5')); 132.2 (d, C(4')); 147.1 (s, C(8')); (Z)-ent-10b: 17.3 (q, MeÀC(3)); 20.6 (q, C(1)); 32.3
(t, C(10')); 38.2 (t, C(9')); 39.7 (t, C(3')); 41.6 (d, C(3)); 43.0 (d, C(1')); 43.1 (d, C(2')); 44.3 (d, C(7')); 55.0
(d, C(6')); 72.0 (d, C(2)); 119.9 (d, C(4)); 131.4 (d, C(5')); 132.4 (d, C(4')); 146.2 (s, C(8')). GC/MS: (E)-ent-
10b: 218 (8, M ), 174 (17), 173 (52), 151 (14), 108 (14), 107 (100), 91 (26), 79 (30), 67 (67); (Z)-ent-10b: 218 (5,
M ), 174 (15), 173 (47), 151 (12), 108 (12), 107 (100), 91 (25), 79 (30), 67 (72).
(2S,3S,4E/Z)-3-Methyl-4-[(1S,2S,6S,7S)-tricyclo[5.2.1.02,6]dec-4-en-8-ylidene]butan-2-ol ((E/Z)-10b). As
described for (E/Z)-ent-10b: (E/Z)-10b 80 :20 (53 mg, 53%, over two steps). Spectral data: corresponding to
those of (E/Z)-ent-10b.
(2S,3S,4E/Z)-3-Methyl-4-[(1R,2R,6R,7R)-tricyclo[5.2.1.02,6]dec-4-en-8-ylidene]butan-2-ol ((E/Z)-ent-
1
10d). As described for (E/Z)-ent-10b: (E/Z)-ent-10d 20 :80 (53 mg, 53%, over two steps). H-NMR: (Z)-ent-
10d: 1.01 (d, J 6.8, MeÀC(3)); 1.03 1.14 (m, HaÀC(10')); 1.12 (d, J 6.4, Me(1)); 1.36 1.48 (m, HbÀC(10'));
1.80 1.90 (m, HaÀC(9')); 1.86 1.98 (m, HaÀC(3')); 2.00 2.26 (m, HÀC(1'), HbÀC(9'), HÀC(2')); 2.50
(ddq, J 9.9, 6.6, 6.6, HÀC(3)); 2.60 (ddddd, J 17.2, 9.7, 2.2, 2.2, 1.5, HbÀC(3')); 2.62 2.74 (m, HÀC(6')); 2.73
(br. s, HÀC(7')); 3.60 (dq, J 6.2, 6.2, HÀC(2)); 4.86 (d, J 9.9, HÀC(4)); 5.47 (dddd, J 5.6, 2.4, 2.4, 2.4,
HÀC(5')); 5.67 (dddd, 5.6, 2.0, 2.0, 2.0, HÀC(4')); (E)-ent-10d: 0.97 (d, J 6.8, MeÀC(3)); 1.14 (d, J 6.4,
Me(1)); 2.40 (br. s, HÀC(7')); 3.57 (dq, J 6.2, 6.2, HÀC(2)); 5.07 (dt, J 9.9, 2.3, HÀC(4)). 13C-NMR: (Z)-
ent-10d: 17.4 (q, MeÀC(3)); 19.7 (q, C(1)); 32.2 (t, C(10')); 38.3 (t, C(9')); 39.7 (t, C(3')); 41.2 (d, C(3)); 42.9
(d, C(1')); 43.0 (d, C(2')); 44.5 (d, C(7')); 55.3 (d, C(6')); 72.0 (d, C(2)); 119.5 (d, C(4)); 131.5 (d, C(5')); 132.2
(d, C(4')); 146.7 (s, C(8')); (E)-ent-10d: 16.7 (q, MeÀC(3)); 20.3 (q, C(1)); 32.0 (t, C(10')); 35.5 (t, C(9')); 39.7
(t, C(3')); 40.8 (d, C(3)); 43.2 (d, C(2')); 43.2 (d, C(1')); 49.4 (d, C(7')); 55.3 (d, C(6')); 72.3 (d, C(2)); 119.2
(d, C(4)); 131.4 (d, C(5')); 132.3 (d, C(4')); 147.3 (s, C(8')). GC/MS: (Z)-ent-10d: 218 (7, M ), 174 (18), 173
(56), 151 (11), 108 (14), 107 (100), 91 (24), 79 (31), 67 (75); (E)-ent-10d: 218 (6, M ), 174 (12), 173 (43), 151
(14), 108 (13), 107 (100), 91 (24), 79 (28), 67 (68).
(2R,3R,4E/Z)-3-Methyl-4-[(1S,2S,6S,7S)-tricyclo[5.2.1.02,6]dec-4-en-8-ylidene]butan-2-ol ((E/Z)-10d). As
described for (E/Z)-ent-10b: (E/Z)-10d 20 :80 (51 mg, 51%, over two steps). Spectral data: corresponding to
those of (E/Z)-ent-10d.
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