1R,3S,6S,7R,10S-7-Isopropyl-4,10-dimethylbicyclo[4.4.0]dec-4-en-3,10-diol (8). Mp 102-103°C (Et O), R 0.28
f
2
(EtOAc), C15H26O2, [α]C26 +49.1° (c 1.0, CHCl ).
3
PMR spectrum (δ, ppm, J/Hz): 0.81 [3H, d, J = 7.0, CH (CH )CH], 0.88 [3H, d, J = 7.0, CH (CH )CH], 1.20 (1H, m,
3
3
3
3
eq
eq
eq
Hax-9), 1.25 (3H, s, CH C-10), 1.37 (1H, m, H-7), 1.50 (3H, m, CH -8 and H -9), 1.67 (1H, dd, Jgem = 9.5, J2-3 = 5.0, J2-1
3
3
was not determined*, Heq-2), 1.73 (1H, m, H-1), 1.75 (3H, s, CH C-4), 1.88 (1H, dqq, JMe2CH-7 = 4.5, JMe2CH-Me = 7.0, Me CH),
3
2
2.05 (1H, m, J6-5 = 5.0, H-6), 2.24 (1H, dd, Jgem = 9.5, J2-3ax = 7.5, Hax-2), 2.50 (1H, br.s, OH), 2.56 (1H, br.s, OH), 4.03 (1H,
dd, J3-2eq = 5.0, J3-2ax = 7.5, H-3), 5.54 (1H, qd, J5-Me = 1.5, J5-6 = 5.0, H-5). 13C NMR spectrum (δ, ppm): 16.22 (CH ), 19.62
3
(CH ), 21.15 (C-8), 21.70 (CH ), 26.47 (Me C), 27.74 (CH ), 29.80 (C-2), 35.13 (C-9), 37.18 (C-6), 43.32 (C-7), 44.40 (C-1),
3
3
2
3
70.72 (C-3), 72.07 (C-10), 128.37 (C-5), 137.29 (C-4).
1R,3R,6S,7R,10S-7-Isopropyl-4,10-dimethylbicyclo[4.4.0]dec-4-en-3,10-diol (9). Mp 69-71°C (Et O), R 0.26
f
2
(EtOAc), [α]D22 +93° (c 1.0, CHCl ).
3
PMR spectrum (δ, ppm, J/Hz): 0.78 [3H, d, J = 7.0, CH (CH )CH], 0.82 [3H, d, J = 7.0, CH (CH )CH], 1.05 (1H, m,
3
3
3
3
H-9), 1.22 (3H, s, CH C-10), 1.27 (1H, m, Hax-8), 1.42 (1H, m, Heq-9), 1.47 (1H, m, Heq-8), 1.68 (1H, td, J2-3ax = 4.4,
3
J2-1ax = 4.4, Jgem = 10.1, Hax-2), 1.72 (1H, d, JMe-5 = 1.5, CH C-4), 1.78 (1H, m, J2-3eq = 1.7, J2-1eq was not determined,
3
Jgem = 10.1, Heq-2), 1.82 (1H, m, H-7), 1.87 (1H, dqq, JMe2CH-7 = 3.2, JMe2CH-Me = 7.0, Me CH), 1.95 (1H, m, H-1), 2.0 (1H, m,
2
H-6), 3.94 (1H, dd, J3-2eq = 1.7, J3-2ax = 4.4, H-3), 5.65 (1H, qd, J5-Me = 1.5, J5-6 = 5.6, H-5). 13C NMR spectrum (δ, ppm): 15.36
(CH ), 21.02 (CH ), 21.33 (C-8), 21.53 (CH ), 26.80 (C-13), 28.01 (C-2), 28.06 (CH ), 34.59 (C-9), 36.97 (C-6), 39.62 (C-7),
3
3
3
3
42.56 (C-1), 68.36 (C-3), 71.77 (C-10), 129.02 (C-5), 134.70 (C-4).
b. In DMSO
(+)-δ-Cadinol was oxidized at 100°C by a procedure analogous to that above using DMSO as the solvent. After the
reaction was finished (TLC monitoring), the reaction mixture was diluted with saturated NaCl solution (5 mL) and extracted
with EtOAc (3×5 mL). The extracts were dried over MgSO . The solvent was removed in a rotary evaporator. The solid was
4
chromatographed to give a mixture of diastereomeric 8 and 9 in 74% yield and a 5:95 ratio.
c. In t-butanol
(+)-δ-Cadinol was oxidized at 80°C by a procedure analogous to that above using t-BuOH as the solvent to give 9 in
77% yield.
1R,3S,6S,7R,10S-3-Benzyloxy-7-isopropyl-4,10-dimethylbicyclo[4.4.0]dec-4-en-10-ol (10) and 1R,3R,6S,7R,10S-3-
benzyloxy-7-isopropyl-4,10-dimethylbicyclo[4.4.0]dec-4-en-10-ol (11). A solution of dimsyl sodium that was prepared by
adding NaH (0.05 g, 1.1 mmole) to DMSO (5 mL) under Ar was added dropwise to a solution of a mixture of 8 and 9 (0.13 g,
0.54 mmole, 43:57 ratio) in DMSO (5 mL). The reaction mixture was stirred at room temperature for 30 min and treated with
BnCl (0.13 mL, 1.1 mmole). After the reaction was finished (TLC monitoring), the mixture was poured into icewater (10 mL)
and extracted with EtOAc (3×10 mL). The extracts were combined, dried over MgSO , and evaporated in a rotary evaporator.
4
The solid was chromatographed to give 10 (0.07 g, 40%) and 11 (0.1 g, 54%).
α-Epimer 10. Mp 97-99°C (Et O), Rf 0.30 (hexane—EtOAc, 7:1), C22H32O2, [α]D22 +54.6° (c 1.0, CHCl ).
2
3
PMR spectrum (δ, ppm, J/Hz): 0.82 [3H, d, J = 6.9, CH (CH )CH], 0.9 [3H, d, J = 6.9, CH (CH )CH], 1.15 (1H, ddd,
3
3
3
3
J = 3.4, J = 4.0, and J = 11.2, H-8), 1.28 (3H, s, CH C-10), 1.48 (1H, m, J = 3.0, H-7), 1.50 (3H, m, CH -9, H-8), 1.68 (1H, m,
3
2
H-1), 1.78 (3H, s, CH C-4), 1.98 (1H, dqq, J = 3.0 and J = 6.9, HCMe ), 2.05 (1H, m, H-6), 2.30 (1H, m, Jgem = 10.0, H-2), 2.46
3
2
(1H, ddd, J = 1.0, J = 6.3, and Jgem = 10.0, H-2), 3.96 (1H, dd, J = 6.3 and J = 8.4, H-3), 4.51 (1H, d, J = 11.5, OCH Ph), 4.70
2
(1H, dd, Jgem = 11.5 and J = 10.4, OCH Ph), 5.67 (1H, d, J = 5.4, H-5), 7.38 (5H, m, Ph). 13C NMR spectrum (δ, ppm): 15.24
2
(CH ), 19.76 (CH ), 21.32 (C-8), 21.46 (CH ), 24.80 (C-2), 26.32 (CH ), 27.68 (HCMe ), 35.06 (C-9), 36.88 (C-6), 43.68 (C-7),
3
3
3
3
2
44.10 (C-1), 70.42 (OCH Ph), 71.83 (C-10), 78.22 (C-3), 128.80 (C-5), 135.48 (C-4), 127.35, 127.66, 128.33, 138.69 (Ph).
2
β-Epimer 11. Oil, R 0.28 (hexane—EtOAc, 7:1), [α]D20 +42.3° (c 1.0, CHCl ).
f
3
PMR spectrum (δ, ppm, J/Hz): 0.82 [3H, d, J = 6.9, CH (CH )CH], 0.90 [3H, d, J = 6.9, CH (CH )CH], 1.10 (1H, m,
3
3
3
3
H-8), 1.28 (3H, s, CH C-10), 1.48 (1H, m, H-7), 1.50 (3H, m, CH -9, H-8), 1.58 (1H, m, H-1), 1.78 (3H, s, CH C-4), 1.92 (1H,
3
2
3
m, HCMe ), 1.94 (1H, dd, J = 2.9, Jgem = 14.1, Hax-2), 2.05 (1H, m, H-6), 2.28 (1H, d, Jgem = 14.1, Heq-2), 3.72 (1H, d, J = 2.9,
2
H-3), 4.51 (1H, d, J = 12.0, OCH Ph), 4.70 (1H, d, J = 12.0, OCH Ph), 5.75 (1H, d, J = 5.1, H-5), 7.38 (5H, m, Ph). 13C NMR
2
2
spectrum (δ, ppm): 15.39 (CH ), 21.26 (CH ), 21.39 (C-8), 24.63 (CH ), 23.08 (C-2), 26.80 (CH ), 28.16 (HCMe ), 34.68
3
3
3
3
2
______
*J2-1eq could not be determined by double resonance because of signal overlap.
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