二、海洋甾体化合物 二、海洋甾体化合物 1皂苷类 o6g 海参皂苷 海星皂苷 wo. nakfanlktseandaccn a Marine Sterol Side-Chains(N-Nueleus) Unusual Marine Steroids yed 8 Unusual Marine Steroids 甾体化合物Sterols SO,NHMS 8 9 9 171 二、 海洋甾体化合物 A single general formula can describe most terrestrial sterols (1-3). 1 R = H, Cholesterol (1) 2 R = Me, 24-MethylCholesterol (2) 3 R = Et, 24-EthylCholesterol (3) HO 17 19 1 11 5 R 24 A B C D 172 二 、 海洋甾体化合物 1 皂苷类 海参皂苷 海星皂苷 1955年Yamanouchi首次从海参中分得海参素-B, 直到1978年Kitagawa测定出海参素-B的结构。 海参和海星是从动物中分离皂苷的第一资源 Minale. L. Chem.Rev. 1993, 93:1839-1895 Fattorusso E. Steroids from sponges: Recent reports. Steroids. 1999, 64:687-714. O O OH HO OO O O OH OH OH OH NaO3SO Echinoside B OH O-Xyl OH OH OH NaO3SO Aphelasteroside A 173 N17 24 23-Methyl-22,23-methylene￾Cholesterol (1) N17 24 Dihydrocalysterol (2) N17 24 Calysterol (3) N17 24 23H-Isocalysterol (4) N17 N 5 6 Marine Sterol Side Marine Sterol Side-Chains (N=Nucleus) Chains (N=Nucleus) 陆生植物产生的甾醇通常与b-谷甾醇密切相关，海洋生物中含有 大量异常的甾醇，大多是在侧链不同位置上烷基化，C-22 or 23. 174 Unusual Marine Steroids HO O O O HO H H O OH OH H H Nephthea chabrolii was the source of the 3-keto-steroids chabrolosteroids A and B and unusual spiro-steroid chabrolosteroid C. J.-H. Su, F.-Y. Lin, H.-C. Huang, C.-F. Dai, Y.-C. Wu, W.-P. Hu, C.-H. Hsu and J.-H. Sheu, Tetrahedron, 2007, 63, 703. 175 Unusual Marine Steroids 9,11-Seco-steroids 8,9-Seco-steroids Degraded Steroids HO 17 19 1 5 24 A B C D MeO 17 19 1 11 5 24 A B D HO H O 17 11 24 C D O O MeO 17 11 24 C D O O MeO 176 甾体化合物 Sterols Sterols Marine organisms have been found to be storehouses of sterols, particularly in terms of unique side-chain structures and unusual functionalization. • Sulfamate group in haplosamate A have only been found in nature as metabolite of marine sponges. Haplosamate A Faulkner D. J. Tetrahedron. 1999, 55, 8323. O OH NaO3SO OH OH OSO2NHMe