5
acetate 9.7/ 0.3) provided 3a (236 mg, 70 %) as a colorless oil;
[α]D20 +10.7 (c 1.0, CH2Cl2); 1H NMR (250.13 MHz, CDCl3) δ =
0.83 (s, 3H, H-14), 1.03-1.22 (m, 7H), 1.33 (ddd, 1H, J = 13.4,
3.5, 3.3 Hz), 1.40-1.48 (m, 1H), 1.48-1.53 (m, 1H), 1.57 (dd, 1H,
J = 13.4, 3.3 Hz), 1.77-1.84 (m, 1H), 1.87 (ddd, 1H, J = 12.1, 6.7,
3.1 Hz), 1.94 (dd, 1H, J = 15.1, 6.1 Hz), 2.43 (dddd, 1H, J =
12.1, 12.0, 3.9, 3.9 Hz), 2.86 (bs, 1H, H-3), 3.70 (s, 3H, CO2Me),
5.50 (s, 1H, H-13), 6.09 (s, 1H, H-13); 13C NMR (62.9 MHz,
CDCl3) δ = 16.5 (C-14), 21.3 (C-15), 21.7 (CH2), 27.3 (CH2),
30.1 (CH2), 31.6 (C-10), 34.8 (CH2), 39.8 (CH2), 40.7 (C-7), 48.2
(C-5), 52.1 (OMe), 58.8 (C-4), 61.1 (C-3), 123.1 (C-13), 145.5
(C-11), 168.0 (C-12); HRMS (ESI): calcd. For C16H25O3 [M +
H]+ 265.1800; found 265.1798.
13), 145.6 (C-11), 168.0 (C-12), 213.2 (C-3); HRMS (ESI):
ACCEPTED MANUSCRIPT
calcd. For C16H25O3 [M + H]+ 265.1800; found 265.1798.
5.9. (1S,4aS,7R,8aS)-7-(3-hydroxyprop-1-en-2-yl)-1,4a-
dimethyldecahydronaphthalen-2-ol (4b).2a
Following the general reduction with DiBAlH with 4a (165 mg,
0.6 mmol). Column chromatography on silica gel
(petroleum ether/ ethyl acetate 6/4) provided 4b ( 120 mg, 81 %)
as a colorless oil; [α]D -8.2 (c 1.0, CHCl3) lit [α]D -25 (c 1.4,
CHCl3); H NMR (250.13 MHz, CDCl3) δ = 0.82 (s, 1.5 H, H-
14), 0.83 (s, 1.5H, H-14), 0.87 (d, 1H, J = 6.7 Hz), 0.92 (d, 1H, J
= 6.7 Hz), 0.95-1.29 (m, 5H), 1.30-1.68 (m, 7H), 1.68-1.81 (m,
1H), 1.82-1.99 (m, 1H), 2.19 (bs, 2H), 3.07 (ddd, 0.5H, J = 10.5,
10.3, 5.1 Hz), 3.72-3.77 (m, 0.5H), 4.07 (bs, 2H, H-12), 4.86 (bs,
1H, H-13), 4.99 (bs, 1H, H-13); 13C NMR (62.9 MHz, CDCl3) δ
= 15.0 (CH3), 16.1 (CH3), 16.1 (CH3), 17.0 (CH3), 27.2 (CH2),
27.4 (CH2), 29.1 (CH2), 29.9 (CH2), 30.0 (CH2), 30.9 (CH2), 33.3
(C-10), 33.6 (C-10), 35.3 (CH2), 35.5 (CH), 39.3 (CH), 39.6
(CH2), 41.7 (CH2), 41.8 (CH2), 41.9 (CH), 42.2 (CH), 43.1 (CH),
49.1 (CH), 65.0 (C-12), 65.0 (C-12), 72.3 (C-3), 107.5 (C-13),
107.8 (C-13), 154.2 (C-11), 154.4 (C-11); HRMS (ESI): calcd.
For C15H26LiO2 [M + Li]+ 245.2091; found 245.2087.
20
20
1
5. 6. 2-[(1aR,3aS,6R,7aR,7bS)-3a,7b-
dimethyldecahydronaphtho[1,2-b]oxiren-6-yl]prop-2-en-1-ol
(3b).
Following the general reduction with DiBAlH with 3a (235 mg,
0.9 mmol). Column chromatography on silica gel
(petroleum ether/ ethyl acetate 8/2) provided 3b (170 mg, 81 %)
1
as a colorless oil; [α]D20+46.4 (c 1.0, CH2Cl2); H NMR (250.13
MHz, CDCl3) δ = 0.77 (s, 3H, H-14), 1.03-1.16 (m, 3H), 1.18 (s,
3H, H-15), 1.23 (d, 1H, J = 12.7 Hz), 1.34 (ddd, 1H, J = 13.4,
3.5, 3.1 Hz), 1.39-1.58 (m, 3H), 1.76-1.84 (m, 1H), 1-84-1.90 (m,
1H), 1.90-2.01 (m, 2H), 2.25 (bs, 1H, OH), 2.89 (s, 1H, H-3),
4.06 (s, 2H, H-12), 4.88 (s, 1H, H-13), 5.01 (s, 1H, H-13); 13C
NMR (62.9 MHz, CDCl3) δ = 16.4 (C-14), 21.2 (C-15), 21.6
(CH2), 27.4 (CH2), 30.0 (CH2), 31.6 (C-10), 34.8 (CH2), 39.8
(CH2), 42.3 (C-7), 48.2 (C-5), 59.0 (C-4), 61.2 (C-3), 65.2 (C-
12), 108.1 (C-13), 154.0 (C-11); HRMS (ESI): calcd. For
C15H25O2 [M + H]+ 237.1850; found 237.1849.
5.10. 2-[(2R,4aS,8S,8aS)-4a,8-dimethyl-7-
oxodecahydronaphthalen-2-yl]acrylaldehyde (4c).
Following the general procedure of oxidation with PDC with 4b
(90 mg, 0.4 mmol). Column chromatography on silica gel
(petroleum ether/ ethyl acetate 8/2) provided 4c (64 mg, 72 %) as
20
1
a colorless oil; [α]D +39.4 (c 1.0, CH2Cl2). H NMR (250.13
MHz, CDCl3) δ = 1.04 (d, 3H, J= 8.1 Hz; H-15), 1.13 (s, 3H, H-
14), 1.16-1.39 (m, 2H), 1.40-1.67 (m, 5H), 1.68-1.83 (m, 2H),
2.18-2.31 (m, 1H), 2.32-2.43 (m, 1H, H-4), 2.45-2.56 (m, 1H, H-
7), 2.57-2.74 (m, 1H), 5.99 (s, 1H, H-13), 6.28 (s, 1H, H-13),
9.51 (s, 1H, H-12); 13C NMR (62.9 MHz, CDCl3) δ = 13.8 (C-
15), 19.0 (C-14), 27.1 (CH2), 31.3 (CH2), 33.5 (C-10), 35.4
(CH2), 36.9 (CH2), 40.3 (C-7), 42.9 (CH2), 46.5 (C-5), 49.2 (C-
4), 133.5 (C-13), 154.8 (C-11), 194.8 (C-12), 216.0 (C-3);
HRMS (ESI): calcd. For C15H23O2 [M + H]+ 235.1691; found
235.1692.
5.7. 2-[(1aR,3aS,6R,7aR,7bS)-3a,7b-
dimethyldecahydronaphtho[1,2-b]oxiren-6-yl]acrylaldehyde
(3c).
Following the general procedure of oxidation with PDC with 3b
(181 mg, 0.8 mmol). Column chromatography on silica gel
(petroleum ether/ ethyl acetate 9.5/0.5) provided 3c (134 mg, 74
20
1
%) as a colorless oil; ([α]D +4.3 (c 1.0, CH2Cl2); H NMR
(250.13 MHz, CDCl3) δ = 0.80 (s, 3H, H-14), 1.06-1.26 (m, 7H),
1.36 (ddd, 1H, J = 13.3, 3.3, 3.3 Hz), 2.41-2.56 (m, 2H), 1.61
(dd, 1H, J = 13.4, 3.3 Hz), 1.75-1.82 (m, 1H), 1.83-1.94 (m, 1H),
1.95-2.01 (m, 1H), 2.48 (dddd, 1H, J = 11.9, 11.9, 4.2, 4.1), 2.89
(bs, 1H, H-3), 5.96 (s, 1H, H-13), 6.25 (s, 1H, H-13), 9.50 (s, 1H,
H-12); 13C NMR (62.9 MHz, CDCl3) δ = 16.4 (C-14), 21.2 (C-
15), 21.7 (CH2), 26.8 (CH2), 29.4 (CH2), 31.6 (CH2), 34.8 (C-10),
37.5 (CH2), 39.7 (C-7), 48.1 (C-5), 58.7 (C-4), 61.0 (C-3), 133.4
(C-13), 155.0 (C-11), 194.8 (C-12); HRMS (ESI): calcd. For
C15H23O2 [M + H]+ 235.1689; found 235.1692.
5.11. Methyl
methylenedecahydronaphthalen-2-yl]acrylate
methyl 2-[(3aR,5R,7aS)-3-formyl-3,7a-dimethyloctahydro-
1H-inden-5-yl]acrylate (6).
2-[(2R,4aS,7R,8aR)-7-hydroxy-4a-methyl-8-
(5a)2c
and
Following the general procedure for acid-promote ring opening
of epoxide with 3a (478 mg, 1.8 mmol) and Bi(OTf)3. Column
chromatography on silica gel (petroleum ether/ ethyl acetate
6/4) provided 5a (268 mg, 56 %) as a colorless oil and 6 (152
mg, 32%) as a colorless oil.
5a: [α]D20 +35.3 (c 1.0, CH2Cl2); 1H NMR (250.13 MHz, CDCl3)
δ = 0.60-0.73 (m, 3H, H-14), 1.15-1.29 (m, 2H), 1.32-1.64 (m,
5H), 1.66-1.90 (m, 4H), 2.33-2.46 (m, 1H, H-5), 2.47-2.62 (m,
1H, H-7), 3.72 (s, 3H, OMe), 4.25 (dd, 1H, J = 2.5, 2.4 Hz, H-3),
4.52 (s, 1H, H-15), 4.89 (s, 1H, H-15), 5.53 (s, 1H, H-13), 6.12
(s, 1H, H-13); 13C NMR (62.9 MHz, CDCl3) δ = 15.8 (C-14),
27.4 (CH2), 29.8 (CH2), 29.9 (CH2), 35.9 (CH2), 36.1 (C-10),
39.9 (C-7), 40.9 (CH2), 43.9 (C-5), 52.0 (OMe), 73.7 (C-3), 109.2
(C-15), 122.9 (C-13), 146.0 (C-11), 152.0 (C-4), 168.1 (C-12);
HRMS (ESI): calcd. For C16H24LiO3 [M + Li]+ 271.1881; found
271.1880.
5.8. Methyl
oxodecahydronaphthalen-2-yl]acrylate (4a).
2-[(2R,4aS,8S,8aS)-4a,8-dimethyl-7-
Following the general procedure for acid-promote ring opening
of epoxide with 3a (225 mg, 0.9 mmol) and BF3.Et2O. Column
chromatography on silica gel (petroleum ether/ ethyl acetate
8/2) provided 4a (156 mg, 69 %) as a white solid; mp = 121 –
20
123 °C; [α]D -1.9 (c 1.0, CH2Cl2). 1H NMR (250.13 MHz,
CDCl3) δ = 1.00 (d, 3H, J = 6.5 Hz, H-15), 1.14 (s, 3H, H-14),
1.17-1.36 (m, 3H), 1.49-1.57 (m, 3H), 1.57-1.66 (m, 1H, H-5),
1.73-1.80 (m, 2H), 2.19-2.28 (m, 1H, H-4), 2.27-2.35 (m, 1H),
2.36-2.44 (m, 1H, H-7), 2.55 (dddd, 1H, J = 14.1, 14.1, 6.5, 0.9
Hz), 3.78 (s, 3H, OMe), 5.58 (s, 1H, H-13), 6.18 (s, 1H, H-13);
13C NMR (62.9 MHz, CDCl3) δ = 11.3 (C-15), 16.5 (C-14), 27.0
(CH2), 31.3 (CH2), 33.5 (C-10), 38.1 (CH2), 39.7 (C-7), 40.8
(CH2), 41.3 (CH2), 45.7 (C-4), 51.1 (C-5), 51.9 (OMe), 123.3 (C-
6: [α]D20 -3.2 (c 1.0, CH2Cl2); 1H NMR (250.13 MHz, CDCl3) δ =
1.00 (s, 3H, Me-7a’), 1.07 (s, 3H, Me-3’), 1.12-1.56 (m, 5H),
1.60-1.71 (m, 4H), 1.76 (ddd, 1H, J = 12.4, 3.1, 3.1 Hz), 2.06-
2.13 (m, 1H), 2.54 (dddd, 1H, J = 12.4, 12.4, 4.2, 4.2 Hz), 3.74
(s, 3H, OMe), 5.57 (s, 1H), 6.14 (d, 1H, J = 1.2 Hz), 9.36 (s, 1H).
13C NMR (62.9 MHz, CDCl3) δ = 16.7 (Me-3’), 19.3 (Me-7a’),