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6b-Benzoxy-1,2b-epoxy-8ab-methyl-4aa-decahydronaphthalene (15b):
1H-NMR d: 8.03 (2H, dd, Jꢁ8.6, 1.5, o-), 7.55 (1H, tt, Jꢁ7.3, 2.0, p-), 7.43
(2H, t, Jꢁ7.9, m-), 4.98 (1H, tt, Jꢁ11.2, 5.5, C3-H), 3.20 (1H, br s, C8-H or
C9-H), 2.81 (1H, d, Jꢁ3.7, C9-H or C8-H), 2.15 (1H, dd, Jꢁ15.0, 4.8), 1.05
(3H, s, CH3). 13C-NMR d: 166.07, 132.80, 130.65, 129.52, 128.27, 73.78,
61.02, 53.89, 41.35, 36.37, 32.69, 32.52, 27.13, 26.62, 22.29, 13.73. LR-MS
(FAB) m/z: 287 ([MꢄH]ꢄ), HR-MS (FAB) Calcd for C18H23O3 ([MꢄH]ꢄ):
287.1647; Found: 287.1636.
7b-Benzoxy-4ab-methyl-4a,5,6,7,8,8aa-hexahydro-1H-naphthalen-2-one
(16): 1H-NMR d: 8.04 (2H, dd, Jꢁ8.6, 1.5, o-), 7.56 (1H, tt, Jꢁ7.3, 2.2, p-),
7.44 (2H, t, Jꢁ7.3, m-), 6.81 (1H, d, Jꢁ9.9, C3-H), 5.88 (1H, d, Jꢁ9.9, C4-
H), 5.01 (1H, tt, Jꢁ11.2, 5.1, C7-H), 1.17 (3H, s, CH3). 13C-NMR d:
199.17, 165.91, 160.06, 132.91, 130.39, 129.51, 128.30, 127.29, 72.70,
40.51, 40.14, 35.46, 35.41, 32.76, 26.98, 16.44. IR (KBr) cmꢀ1: 1717, 1672,
1281. LR-MS (EI) m/z: 284 (Mꢄ), HR-MS (EI) Calcd for C18H20O3:
284.1412; Found: 284.1390.
Reduction of 10 to 8b This stereoselective reduction was carried out
according to the well-known procedure for steroids.28) To a solution of
111 mg of 10 (0.39 mmol) in 4 ml of dichloromethane was added a solution
of 282 mg of cerium(III) chloride heptahydrate (0.76 mmol) in 1.5 ml of
methanol. The resulting solution was stirred at ꢀ78 °C, and 32 mg of
sodium borohydride (0.85 mmol) was added. Stirring was continued for 1 h,
then the mixture was poured into 5% hydrochloric acid, and extracted with
ether. The combined organic layer was washed with brine, dried over magne-
sium sulfate, and filtered. The solvent was removed with a rotary evaporator,
and the residue was flash-chromatographed (ethyl acetate : hexaneꢁ1 : 4 then
1 : 1) to afford 105 mg of 8b (94%). The stereoselective reduction of 13 and
16 were performed with similar procedure.
(10): Colorless prisms (recryst from ethyl acetate–hexane) mp: 115.5—
116.5 °C H-NMR d 8.05 (2H, dd, Jꢁ7.0, 1.5, o-), 7.58 (1H, tt, Jꢁ7.3, 2.0,
1
m-), 5.83 (1H, d, Jꢁ2.0, C6-H), 5.02 (1H, tt, Jꢁ11.4, 4.8, C3-H), 2.75 (1H,
ddd, Jꢁ14.1, 5.1, 2.2), 2.40 (1H, dt, Jꢁ17.4, 3.7), 1.53 (1H, dt, Jꢁ3.85,
13.8), 1.33 (3H, s, CH3). 13C-NMR d: 199.04, 165.75, 165.56, 133.06,
130.18, 129.57, 128.36, 126.41, 72.82, 38.19, 37.94, 37.31, 35.14, 33.87,
27.37, 21.96. IR (KBr) cmꢀ1: 1720, 1672, 1275. LR-MS (EI) m/z: 284 (Mꢄ),
HR-MS (EI) Calcd for C18H20O3: 284.1412; Found: 284.1426. Anal. Calcd
for C18H20O3: C, 76.03; H, 7.09. Found: C, 75.98; H, 7.17.
5b-Benzoxy-4ab-methyl-2,3,4,4a,5,6,7,8-octahydronaphthalen-2a-ol
1
(11a): H-NMR d: 8.04 (2H, dd, Jꢁ8.4, 1.5, o-), 7.56 (1H, tt, Jꢁ7.3, 2.2,
p-), 7.44 (2H, t, Jꢁ7.3, m-), 5.61 (1H, dd, Jꢁ4.2, 1.7, C6-H), 4.86 (1H, dd,
Jꢁ11.6, 4.6, C1-H), 4.12 (1H, m, C7-H), 1.23 (3H, s, CH3). 13C-NMR d:
165.94, 145.48, 132.86, 130.62, 129.54, 128.35, 124.70, 80.09, 64.70, 39.86,
31.23, 30.30, 27.70, 27.30, 24.25, 18.00. IR (KBr) cmꢀ1: 3464, 1717, 1275.
LR-MS (FAB) m/z: 287 ([MꢄH]ꢄ), HR-MS (FAB) Calcd for C18H23O3
([MꢄH]ꢄ): 287.1647; Found: 287.1637.
5b-Benzoxy-4ab-methyl-2,3,4,4a,5,6,7,8-octahydronaphthalen-2b-ol
1
(11b): H-NMR d: 8.03 (2H, dd, Jꢁ8.4, 1.5, o-), 7.56 (tt, Jꢁ7.3, 2.2, p-),
7.44 (2H, t, Jꢁ7.3, m-), 5.48 (1H, br s, C6-H), 4.77 (1H, dd, Jꢁ11.6, 4.4,
C1-H), 4.20 (1H, m, C7-H), 1.30 (3H, s, CH3). 13C-NMR d: 165.99, 143.72,
132.89, 130.57, 129.52, 128.37, 126.48, 80.79, 67.41, 39.89, 33.25, 31.14,
28.51, 27.43, 24.34, 18.35. IR (KBr) cmꢀ1: 3412, 1717, 1275. LR-MS
(FAB) m/z: 287 ([MꢄH]ꢄ), HR-MS (FAB) Calcd for C18H23O3 ([MꢄH]ꢄ):
287.1647; Found: 287.1668.
5b-Benzoxy-1,8aa-epoxy-4ab-methyldecahydronaphthalene (12a): 1H-
NMR d: 8.04 (2H, dd, Jꢁ1.5, 8.6, o-), 7.57 (1H, tt, Jꢁ7.5, 1.5, p-), 7.45
(2H, t, Jꢁ7.7, m-), 5.28 (1H, dd, Jꢁ11.4, 4.8, C1-H), 2.99 (1H, d, Jꢁ5.0,
C6-H), 2.13 (1H, dt, Jꢁ4.4, 13.6), 1.26 (3H, s, CH3), 1.05 (1H, br d,
Jꢁ13.2). 13C-NMR d: 165.89, 132.97, 130.42, 129.59, 128.40, 73.64, 63.53,
61.44, 38.85, 30.69, 28.88, 26.59, 23.73, 20.82, 18.17, 15.69. LR-MS (FAB)
m/z: 287 ([MꢄH]ꢄ), HR-MS (FAB) Calcd for C18H23O3 ([MꢄH]ꢄ):
287.1647; Found: 287.1643.
References
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Chem. Pharm. Bull., 47, 64—70 (1999).
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120—125 (2000).
5b-Benzoxy-1,8ab-epoxy-4ab-methyldecahydronaphthalene (12b): 1H-
NMR d: 8.02 (2H, br d, Jꢁ7.0, o-), 7.55 (1H, tt, Jꢁ7.5, 2.0, p-), 7.43 (2H, t,
Jꢁ7.3, m-), 5.09 (1H, dd, Jꢁ11.0, 5.0, C1-H), 2.97 (1H, t, Jꢁ2.0, C6-H),
1.31 (3H, s, CH3), 0.98 (1H, br d, Jꢁ11.2). 13C-NMR 165.87, 132.76,
130.74, 129.52, 128.31, 79.00, 64.93, 59.04, 38.22, 29.99, 29.22, 26.93,
22.07, 20.48, 16.22, 15.25. LR-MS (FAB) m/z: 287 ([MꢄH]ꢄ), HR-MS
(FAB) Calcd for C18H23O3 ([MꢄH]ꢄ): 287.1647; Found: 287.1639.
5b-Benzoxy-4ab-methyl-4,4a,5,6,7,8-hexahydro-3H-naphthalen-2-one
(13): The spectral data are identical to those reported.31) 1H-NMR d: 8.05
(2H, dd, Jꢁ8.4, 1.5, o-), 7.59 (1H, tt, Jꢁ7.3, 2.2, p-), 7.46 (2H, t, Jꢁ7.3,
m-), 5.86 (1H, d, Jꢁ1.8, C6-H), 4.92 (1H, dd, Jꢁ11.6, 4.4, C1-H), 1.44 (3H,
s, CH3). 13C-NMR d: 198.90, 166.60, 165.74, 133.17, 130.14, 129.56,
128.47, 125.90, 79.75, 40.74, 34.13, 33.48, 31.80, 26.95, 22.94, 16.92. IR
(KBr) cmꢀ1: 1672, 1275, 1717. LR-MS (EI) m/z: 284 (Mꢄ), HR-MS (EI)
Calcd for C18H20O3: 284.1412; Found: 284.1400.
7b-Benzoxy-4ab-methyl-1,2,4a,5,6,7,8,8aa-octahydronaphthalen-2a-ol
1
(14a): H-NMR d: 8.04 (2H, dd, Jꢁ8.4, 1.5, o-), 7.55 (1H, tt, Jꢁ7.3, 1.5,
p-), 7.43 (2H, t, Jꢁ7.3, m-), 5.76 (1H, d, Jꢁ9.9, C9-H), 5.66 (1H, ddd,
Jꢁ9.7, 4.2, 1.3, C8-H), 5.03 (1H, tt, Jꢁ11.2, 5.3, C3-H), 4.17 (1H, t, Jꢁ4.2,
C7-H), 0.95 (3H, s, CH3). 13C-NMR d: 166.01, 142.41, 132.76, 130.74,
129.53, 128.26, 125.76, 73.94, 64.33, 36.05, 35.17, 34.65, 34.61, 33.16,
27.22, 17.26. IR (KBr) cmꢀ1: 3410, 1717, 1277. LR-MS (FAB) m/z: 287
([MꢄH]ꢄ), HR-MS (FAB) Calcd for C18H23O3 ([MꢄH]ꢄ): 287.1647;
Found: 287.1661.
7b-Benzoxy-4ab-methyl-1,2,4a,5,6,7,8,8aa-octahydronaphthalen-2a-ol
1
(14b): H-NMR d: 8.04 (2H, dd, Jꢁ8.4, 1.5, o-), 7.55 (1H, tt, Jꢁ7.5, 2.2,
p-), 7.43 (2H, t, Jꢁ7.9, m-), 5.61 (1H, dd, Jꢁ10.1, 1.5, C8-H or C9-H), 5.50
(1H, br d, Jꢁ10.1, C9-H or C8-H), 4.98 (1H, tt, Jꢁ10.8, 5.3, C3-H), 4.38
(1H, br d, Jꢁ8.8, C7-H), 1.05 (3H, s, CH3). 13C-NMR d: 166.03, 140.06,
132.77, 130.61, 129.49, 128.25, 128.21, 73.72, 68.57, 39.28, 36.26, 35.31,
34.60, 33.21, 27.08, 18.75. IR (KBr) cmꢀ1: 3438, 1717, 1277. LR-MS
(FAB) m/z: 287 ([MꢄH]ꢄ), HR-MS (FAB) Calcd for C18H23O3 ([MꢄH]ꢄ):
287.1647; Found: 287.1632.
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Pharm. Bull., 52, 756—759 (2004).
22) Fraga B. M., Nat. Prod. Rep., 19, 650—672 (2002).
23) Zheng G., Chen J., Fang L., Tang Z., Li Y., Tetrahedron, 60, 6177—
6182 (2004).
24) Ali A., Thompson C. F., Balkovec J. M., Graham D. W., Hammond M.
L., Quraishi N., Tata J. R., Einstein M., Ge L., Harris G., Kelly T. M.,
Mazur P., Pandit S., Santoro J., Sitlani A., Wang C., Williamson J.,
6b-Benzoxy-1,2a-epoxy-8ab-methyl-4aa-decahydronaphthalene (15a):
1H-NMR d: 8.03 (2H, dd, Jꢁ8.6, 1.5, o-), 7.54 (1H, tt, Jꢁ7.3, 1.5, p-), 7.42
(2H, t, Jꢁ7.3, m-), 4.95 (1H, tt, Jꢁ10.8, 5.1, C3-H), 3.13 (1H, t, Jꢁ4.0, C8-
H or C9-H), 2.82 (1H, d, Jꢁ4.0, C9-H or C8-H), 1.04 (3H, s, CH3). 13C-
NMR d: 165.93, 132.71, 130.75, 129.49, 128.24, 73.56, 61.78, 52.45, 34.29,
33.38, 33.15, 33.12, 27.06, 23.13, 22.22, 15.10. LR-MS (FAB) m/z: 287
([MꢄH]ꢄ), HR-MS (FAB) Calcd for C18H23O3 ([MꢄH]ꢄ): 287.1647;
Found: 287.1658.