5472
and (+)-drim-7-en-11-ol ((+)-19), respectively. Oxidation with pyridinium chlorochromate (PCC)
led to the desired aldehyds (+)-albicanal ((+)-1) and (^)-drim-7-en-11-al ((^)-6).
Acknowledgements
Support of this research by a grant of the Deutsche Forschungsgemeinschaft is gratefully
acknowledged.
References
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9, 2325±2328.
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4. Mori, K.; Komatsu, M. Bull. Soc. Chim. Belg. 1986, 95, 771±781.
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7. Herlem, D.; Kervagoret, J.; Yu, D.; Khuong-Huu, F.; Kende, A. S. Tetrahedron 1993, 49, 607±618.
8. Liapis, M.; Ragoussis, V.; Ragoussis, N. J. Chem. Soc., Perkin Trans. 1 1985, 815±817.
9. Ragoussis, V.; Liapis, M.; Ragoussis, N. J. Chem. Soc., Perkin Trans. 1 1987, 987±992.
10. Morey, J.; Costa, A.; Deya, P. M.; Suner, G.; Saa, J. M. J. Org. Chem. 1990, 55, 3902±3909.
11. Small, G. H.; Engman, A. M.; Hall, S. S. J. Org. Chem. 1975, 40, 3151±3152.
12. Grant, H. N.; Prelog, V.; Sneeden, R. P. A. Helv. Chim. Acta 1963, 46, 415±421.
23
13. 4: Colourless crystals, mp 154ꢀC (sub.), ꢀ +17ꢀ (c 1.7, CHCl3). Ref. 17: [ꢀ]D +18ꢀ (CHCl3). MS m/z (%): 314
D
ꢁ
(68, M+ ), 299 (8), 229 (6), 217 (6), 201 (6), 191 (100), 178 (23), 163 (24), 161 (28), 149 (17), 137 (20), 109 (19), 95
1
(29), 81 (17). HRMS: Calcd for C21H30O2 314.22460. Found 314.2246. H-NMR (500 MHz, C6D6): 6.63 (d, 1H,
2.5 Hz, H-60), 6.31 (dd, 1H, 8.5/2.5 Hz, H-40), 6.24 (d, 1H, 8.5 Hz, H-30), 4.87 (s, 2H, H-12), 2.81 (1H, 15.5/10.2
Hz, H-11), 2.73 (1H, 15.5/1.9 Hz, H-11), 2.29 (m, 1H, H-7), 2.17 (1H, 10.2 Hz, H-9), 1.91 (dd, 1H, 12.8/4.6 Hz, H-
7), 1.74 (d, 1H, 12.6 Hz, H-1), 1.57 (m, 1H, H-6), 1.52 (m, 1H, H-2), 1.40 (m, 1H, H-2), 1.34 (d, 1H, 13.2 Hz, H-3),
1.26 (dd, 1H, 12.8/4.1 Hz, H-6), 1.14 (m, 1H, H-3), 1.04 (m, 1H, H-1), 1.02 (m, 1H, H-5), 0.84 (s, 3H, H-13), 0.80
(s, 3H, H-15), 0.78 (s, 3H, H-14). 13C-NMR (125 MHz, C6D6): 150.0 (C-50), 148.6 (C-8), 147.8 (C-20), 130.1 (C-10),
116.9 (C-60), 115.8 (C-30), 112.7 (C-40), 108.2 (C-12), 56.3 (C-9), 55.6 (C-5), 42.4 (C-3), 40.2 (C-10), 39.2 (C-1), 38.5
(C-7), 33.7 (C-13), 33.7 (C-4), 24.6 (C-6), 23.9 (C-11), 21.7 (C-14), 19.8 (C-2), 14.7 (C-15).
23
14. 5: Yellow crystals, mp 133±134ꢀC (MeOH), ꢀ +65ꢀ (c 0.48, MeOH). Ref. 4: [ꢀ]D +59ꢀ (MeOH). MS m/z (%):
D
ꢁ
312 (58, M+ ), 297 (14), 282 (5), 256 (12), 216 (17), 201 (19), 189 (100), 175 (39), 161 (36), 147 (26), 137 (67), 124
(66), 119 (27), 95 (40), 81 (40). HRMS: Calcd for C21H28O2 312.2089. Found 312.2089. 1H-NMR (500 MHz,
CDCl3): 6.71 (d, 1H, 10.0 Hz, H-30), 6.64 (dd, 1H, 10.0/2.4 Hz, H-40), 6.43 (bs, 1H, H-60), 4.74 (s, 1H, H-12), 4.28
(s, 1H, H-12), 2.55 (m, 2H, H-11), 2.33 (m, 1H, H-7), 1.97 (m, 1H, H-9), 1.73 (m, 1H, H-1), 1.71 (m, 1H, H-7), 1.70
(m, 1H, H-6), 1.55 (m, 1H, H-2), 1.48 (m, 1H, H-2), 1.37 (m, 1H, H-3), 1.31 (m, 1H, H-6), 1.19 (m, 1H, H-3), 1.10
(m, 1H, H-5), 1.06 (m, 1H, H-1), 0.85 (s, 3H, H-13), 0.78 (s, 3H, H-14), 0.74 (s, 3H, H-15). 13C-NMR (125 MHz,
CDCl3): 187.8 (C-50), 187.8 (C-20), 149.3 (C-10), 147.1 (C-8), 136.8 (C-30), 136.0 (C-40), 132.8 (C-60), 108.0 (C-12),
55.4 (C-5), 53.9 (C-9), 41.9 (C-3), 39.7 (C-10), 39.1 (C-1), 37.8 (C-7), 33.6 (C-13), 33.6 (C-4), 24.1 (C-6), 23.0 (C-
11), 21.1 (C-14), 19.3 (C-2), 14.5 (C-15).
22
D
15. 9: Colourless crystals, mp 150±152ꢀC (CHCl3), ꢀ +28ꢀ (c 1.0, CHCl3). Ref. 17: [ꢀ]D +30ꢀ (CHCl3). MS m/z (%):
ꢁ
314 (96, M+ ), 191 (100), 175 (18), 161 (13), 135 (17), 123 (36), 109 (37), 95 (27), 69 (13). HRMS: Calcd. for
C21H30O2 314.22460. Found 314.2246. H-NMR (500 MHz, CDCl3): 6.72 (d, 1H, 2.7 Hz, H-60), 6.58 (d, 1H, 8.5
1
Hz, H-30), 6.49 (dd, 1H, 8.5/2.7 Hz, H-40), 5.37 (bs, 1H, H-7), 2.56 (m, 2H, H-11), 2.32 (bs, 1H, H-9), 1.97 (m, 1H,
H-6), 1.88 (m, 1H, H-1), 1.87 (m, 1H, H-6), 1.54 (m, 1H, H-2), 1.45 (s, 3H, H-12), 1.41 (m, 1H, H-2), 1.41 (m, 1H,
H-3), 1.26 (m, 1H, H-5), 1.17 (m, 1H, H-3), 1.08 (m, 1H, H-1), 0.89 (s, 3H, H-14), 0.86 (s, 3H, H-13), 0.86 (s, 3H,
H-15). 13C-NMR (125 MHz, CDCl3): 149.2 (C-50), 147.0 (C-20), 135.3 (C-8), 131.3 (C-10), 122.3 (C-7), 116.5 (C-60),