Chiral Decalins
Journal of Natural Products, 2006, Vol. 69, No. 11 1537
The filtrate was concentrated in vacuo and purified over a silica gel
column (petroleum ether/AcOEt, 4:1) to afford compound 26 (41 mg,
73%).
3), 38.7 (C-1), 36.0 (C-10), 35.8 (C-7), 33.6 (C-13 or C-14), 32.9 (C-
4), 28.8 (C-11), 27.7 (C-16), 22.8 (C-15), 21.8 (C-13 or C-14), 20.4
(C-6), 18.5 (C-2); EIMS m/z 236 [M]+ (13), 221 [M - Me]+ (100),
206 (19), 151 (6),137 (72), 121 (15), 109 (24), 97 (31), 81 (28), 67
(30), 55 (59), 41 (69).
(2) Starting from 23 with the same procedure as (1), yield: 77%.
Compound 26: colorless needle crystals; mp 132.5-134.6 °C; [R]25
D
-8.0 (c 0.97, CHCl3); [R]25 -8.1 (c 0.97, CHCl3); [R]25 -9.0 (c
578
546
Acknowledgment. The authors are grateful to the National Natural
Science Foundation of China (Grant 20572107), Chengdu Municipal
Bureau of Science & Technology, and the Diao Group for financial
support.
0.97, CHCl3); [R]25 -14.6 (c 0.97, CHCl3); [R]25 -21.1 (c 0.97,
436
365
CHCl3); IR (KBr) νmax 3451, 2965, 2929, 1462, 1384, 1123, 1063, 1037
1
cm-1; H NMR (CDCl3, 600 MHz) δ 3.85 (1H, dt, J ) 9.1, 2.9 Hz),
3.77 (1H, q, J ) 8.5 Hz), 3.22 (1H, dd, J ) 9.0, 7.3 Hz), 1.96-2.05
(1H, m), 1.88-1.94 (1H, m), 1.64-1.68 (3H, m), 1.56-1.62 (3H, m),
1.52 (1H, dt, J ) 13.2, 4.2 Hz), 1.38 (3H, s, Me), 1.17 (1H, dd, J )
12.1, 2.0 Hz), 1.10, 1.02, and 0.79 (each 3H, s, Me); 13C NMR (CDCl3,
150 MHz) δ 80.6, 79.1, 64.0, 58.7, 45.8, 38.6, 36.5, 35.8, 35.4, 28.8,
28.4, 27.6, 27.2, 22.9, 20.1, 15.6; EIMS m/z 252 [M]+ (3), 237 [M -
Me]+ (45), 219 [M - Me - H2O]+ (19), 152 (29), 135 (80), 97 (42),
84 (35), 55 (42), 43 (100).
Supporting Information Available: Experimental data of com-
pounds 13, 15, 17-21, 25, and 29, NMR and selected HRMS spectra
of compounds 2-5, 7, 11, and 13-29, and ORTEP diagrams of 2, 3,
14, 17, 19, 21, 23, and 26. This material is available free of charge via
References and Notes
3â-Mesyloxy-9-epi-ambrox (27). A mixture of 26 (50 mg, 0.20
mmol), pyridine (0.2 mL), and CH2Cl2 (3 mL) was cooled to -5 f 0
°C in an ice/NaCl bath, and then methanesulfonyl chloride (0.05 mL)
was added. The mixture was kept at -5f0 °C for 2 h, and additional
CH2Cl2 was added. The mixture was washed with 5% HCl(aq), water,
saturated aqueous NaHCO3, and brine, dried (MgSO4), filtered, and
concentrated in vacuo. The yellow residue was separated over a silica
gel column to give 27 (61 mg, 93%). Compound 27 (pale yellow cubic
crystals): mp 114.8-116.6 °C; [R]25D -4.8 (c 0.08, CHCl3); IR (KBr)
(1) (a) Hanson, J. R. Nat. Prod. Rep. 2005, 22, 594-602, and previous
reviews in this series. (b) Fraga, B. M. Nat. Prod. Rep. 2005, 22,
465-486, and previous reviews in this series. (c) Connolly, J. D.;
Hill, R. A. Nat. Prod. Rep. 2005, 22, 487-503, and previous reviews
in this series.
(2) (a) Ohloff, G.; Giersch, W.; Pickenhagen, W.; Furrer, A.; Frei, B.
HelV. Chim. Acta 1985, 68, 2022-2029. (b) Ohloff, G. In Fragrance
Chemistry; Theimer, E. T., Ed.; Academic Press: New York, 1982;
pp 535-573.
(3) (a) Sunazuka, T.; Omura, S. Chem. ReV. 2005, 105, 4559-4580. (b)
Jansen, B. J. M.; de Groot, A. Nat. Prod. Rep. 2004, 21, 449-477.
(4) (a) de la Torre, M. C.; Garc´ıa, I.; Sierra, M. A. Chem. Eur. J. 2005,
11, 3659-3667. (b) Hua, D. H.; Huang, X.-D.; Chen, Y.; Battina,
S. K.; Tamura, M.; Noh, S. K.; Koo, S. I.; Namatame, I.; Tomoda,
H.; Perchellet, E. M.; Perchellet, J.-P. J. Org. Chem. 2004, 69, 6065-
6078. (c) Yang, L.; Williams, D. E.; Mui, A.; Ong, C.; Krystal, G.;
van Soest, R.; Andersen, R. J. Org. Lett. 2005, 7, 1073-1076. (d)
Kulcit¸ki, V.; Ungur, N.; Gavagnin, M.; Carbone, M.; Cimino, G.
Eur. J. Org. Chem. 2005, 1816-1822.
(5) (a) Arno´, M.; Gonza´lez, M. A.; Zaragoza´, R. J. J. Org. Chem. 2003,
68, 1242-1251. (b) Rolda´n, E. J. A.-M.; Chahboun, R.; Bentaleb,
F.; Torres, E. C.; Alvarez, E.; Haidour, A.; Lo´pez, J. M. R.; Rolda´n,
R. A.-M.; Houssame, S. E. Synlett. 2004, 2701-2704.
(6) (a) Bolster, M. G.; Jansen, B. J. M.; de Groot, A. Tetrahedron 2001,
57, 5657-5662. (b) Bolster, M. G.; Jansen, B. J. M.; de Groot, A.
Tetrahedron 2001, 57, 5663-5679.
(7) (a) Alvarez-Manzaneda, E. J.; Chahboun, R.; Pe´rez, I. B.; Cabrera,
E.; Alvarez, E.; Alvarez-Manzaneda, R. Org. Lett. 2005, 7, 1477-
1480. (b) Alvarez-Manzaneda, E. J.; Chahboun, R.; Barranco, I.;
Torres, E. C.; Alvareza, E.; Alvarez-Manzaneda, R. Tetrahedron Lett.
2005, 46, 5321-5324. (c) Moulines, J.; Bats, J.-P.; Lamidey, A.-
M.; Silva, N. D. HelV. Chim. Acta 2004, 87, 2695-2705. (d)
Kolympadi, M.; Liapis, M.; Ragoussis, V. Tetrahedron 2005, 61,
2003-2010.
(8) (a) Utenova, B. T.; Gundersen, L.-L. Tetrahedron Lett. 2004, 45,
4233-4235. (b) Villamizar, J.; Fuentes, J.; Salazar, F.; Tropper, E.;
Alonso, R. J. Nat. Prod. 2003, 66, 1623-1627.
(9) (a) Pathak, A.; Aslaoui, J.; Morin, C. J. Org. Chem. 2005, 70, 4184-
4187. (b) Aslaoui, J.; Li, H.; Morin, C. Tetrahedron Lett. 2005, 46,
1713-1716.
(10) (a) Barrero, A. F.; Alvarez-Manzaneda, E. J.; Alvarez-Manzaneda,
R.; Chahboun, R.; Meneses, R.; Cuerva, J. M.; Aparicio, M.; Romera,
J. L. Org. Lett. 2001, 3, 647-650. (b) Barrero, A. F.; Simeon, A.;
Jose, F. Q. M.; Herrador, M. M.; Valdivia, M.; Jimenez, D. J. Org.
Chem. 2002, 67, 2501-2508. (c) Alvarez-Manzaneda, E. J.; Romera,
J. L.; Barrero, A. F.; Alvarez-Manzaneda, R.; Chahboun, R.; Meneses,
R.; Aparicio, M. Tetrahedron 2005, 61, 837-844.
(11) (a) Waters, S. P.; Tian, Y.; Li, Y.-M.; Danishefsky, S. J. J. Am. Chem.
Soc. 2005, 127, 13514-13515. (b) Hagiwara, H.; Hamano, K.;
Nozawa, M.; Hoshi, T.; Suzuki, T.; Kido, F. J. Org. Chem. 2005,
70, 2250-2255. (c) Hagiwara, H.; Takeuchi, F.; Nozawa, M.; Hoshib,
T.; Suzuki, T. Tetrahedron 2004, 60, 1983-1989. (d) Deng, W.-P.;
Zhong, M.; Guo, X.-C.; Kende, A. S. J. Org. Chem. 2003, 68, 7422-
7427.
ν
max 2925, 2858, 1465, 1354, 1334, 1174, 939, 912, 873 cm-1; 1H NMR
(CDCl3, 600 MHz) δ 4.34 (1H, dd, J ) 9.2, 8.0 Hz, H-3), 3.86 (1H,
dt, J ) 8.4, 3.2 Hz, H-12), 3.78 (1H, q, J ) 8.4 Hz, H-12), 3.03 (3H,
s, CH3SO3-), 1.89-2.01 (4H, m), 1.38, 1.14, 1.06 and 0.87 (each 3H,
s, Me); 13C NMR (CDCl3, 150 MHz) δ 90.0, 80.4, 64.0, 58.5, 46.1,
38.9, 38.3, 36.1, 35.5, 35.2, 28.7, 28.5, 27.6, 25.2, 22.7, 20.2, 16.4;
EIMS m/z 330 [M]+ (1), 315 [M - Me]+ (58), 234 [M - CH3SO3H]+
(15), 219 (43), 201 (5), 191 (16), 175 (10), 135 (100).
∆
2(3)-9-epi-Ambrox (28). To a solution of compound 27 (30 mg,
0.09 mmol) in DMF (5 mL) was added anhydrous LiCl (20 mg, 0.47
mmol). The mixture was stirred at 100 °C for 4 h and then cooled to
room temperature. Ethyl acetate was added, and the resulting solution
was washed with water three times and brine, dried over MgSO4, and
filtered. Evaporation in vacuo and purification over a silica gel column
(n-hexane/AcOEt, 50:1) gave 28 (17 mg, 80%) as a colorless oil.
Compound 28: [R]20 -4.3 (c 0.24, CHCl3), [R]20 -5.1 (c 0.24,
D
578
CHCl3), [R]20546 -6.4 (c 0.24, CHCl3), [R]20436 -10.2 (c 0.24, CHCl3),
[R]20365 -13.6 (c 0.24, CHCl3); IR (KBr) νmax 2928, 2866, 1630, 1380,
1132, 1115, 1093, 1055, 1039, 723 cm-1; 1H NMR (CDCl3, 600 MHz)
δ 5.46 (1H, ddd, J ) 9.9, 6.0, 1.6 Hz, H-2), 5.35 (1H, dd, J ) 9.9, 2.7
Hz, H-3), 3.86 (1H, dt, J ) 8.4, 2.7 Hz, H-12), 3.78 (1H, q, J ) 8.4
Hz, H-12), 2.00-2.07 (2H, m, H-1 and H-11), 1.93 (1H, m, H-11),
1.69 (1H, dd, J ) 12.2, 8.2 Hz, H-9), 1.63 (1H, dd, J ) 16.4, 6.0 Hz,
H-1), 1.54-1.60 (3H, m, 1H-6 and 2H-7), 1.50 (1H, dd, J ) 12.5, 2.6
Hz, H-5), 1.39 (3H, s, H-16), 1.35 (1H, m, H-6), 1.11 (3H, s, H-15),
0.98 and 0.88 (each 3H, s, H-13 and H-14); 13C NMR (CDCl3, 150
MHz) δ 137.8 (C-3), 121.6 (C-2), 80.6 (C-8), 63.9 (C-12), 56.9 (C-9),
43.7 (C-5), 38.2 (C-1), 35.1 (C-10), 34.6 (C-7), 34.5 (C-4), 31.7 (C-13
or 14), 29.4 (C-11), 26.9 (C-16), 23.1 (C-15), 22.9 (C-13 or 14), 21.3
(C-6); ESIMS m/z 257.1 [M + Na]+ (90), 235.2 [M + H]+ (100);
HRESIMS m/z [M + H]+ 235.2059 (calcd for C16H27O, 235.2056).
(-)-9-epi-Ambrox (7). To a stainless steel autoclave of 20 mL with
a magnetic stirrer were added a solution of 28 (50 mg) in ethyl acetate
(5 mL) and 10% Pd/C (10 mg). The autoclave was evacuated and
purged with hydrogen three times, and then the pressure of hydrogen
was kept at 4 MPa during the entire reaction process. After 12 h, the
stirring was stopped and the autoclave was vented slowly. Removal of
the Pd/C by filtration and concentration in vacuo gave 7 quantitatively
as a colorless oil. The spectroscopic data were the same as those
published.2a,36 Compound 7: [R]25 -6.2 (c 1.0, CHCl3) (lit.19a [R]25
D
D
(12) (a) Boar, R. B.; Allen, J. Phytochemistry 1973, 12, 2571-2578, and
references therein. (b) Phytochemical and ethnobotanical database.
M.; Khanuja, S. P. S. U.S. Pat. Appl. Publ. US 2004220425, 2004;
Chem. Abstr. 2004, 141, 377242. (d) Kuno, N.; Shinohara, G. PCT
Int. Appl. WO 2002012159, 2002; Chem. Abstr. 2002, 136, 164276.
(13) (a) Barrero, A. F.; Manzaneda, E. A.; Manzaneda, R. R. A.;
Arseniyadis, R. S.; Guittet, E. Tetrahedron 1990, 46, 8161-8168.
(b) Barrero, A. F.; Ha´ıdour, A.; Mun˜oz-Dorado, M.; Akssira, M.;
Sedqui, A.; Mansour, I. Phytochemistry 1998, 48, 1237-1240.
-6.0, c 1.0, CHCl3); IR (KBr) νmax 2924, 2854, 1463, 1260, 1098,
1060, 1048, 1025, 802 cm-1; 1H NMR (CDCl3, 600 MHz) δ 3.85 (1H,
dt, J ) 8.5, 3.0 Hz, H-12), 3.77 (1H, q, J ) 8.5 Hz, H-12), 2.04 (1H,
m, H-11), 1.91 (1H, m, H-11), 1.64 (1H, m, H-2), 1.51-1.59 (4H, m,
H-6, 2H-7, and H-9), 1.39-1.42 (2H, m, H-2 and H-3), 1.37 (3H, s,
H-16), 1.21-1.28 (3H, m, 2H-1 and H-6), 1.19 (1H, dd, J ) 12.4, 1.4
Hz, H-5), 1.15 (1H, ddd, J ) 12.8, 12.8, 4.3 Hz, H-3), 1.10 (3H, s,
H-15), 0.89 and 0.82 (each 3H, s, H-13 and H-14); 13C NMR (CDCl3,
150 MHz) δ 80.8 (C-8), 64.1 (C-12), 59.0 (C-9), 46.7 (C-5), 42.3 (C-