Antonov Alexandr S, Afiyatullov Shamil Sh, Kalinovsky Anatoly I, Ponomarenko Ludmila P, Dmitrenok Pavel S, Aminin Dmitry L, Agafonova Irina G, Stonik Valentin A
Pacific Institute of Bioorganic Chemistry, Far-Eastern Branch of the Russian Academy of Sciences, Prospect 100 let Vladivostoku, 690022 Vladivostok, Russian Federation.
J Nat Prod. 2003 Aug;66(8):1082-8. doi: 10.1021/np0300030.
New steroidal oligoglycosides mycalosides B-I (2-9) have been isolated from the polar extract of the Caribbean sponge Mycale laxissima, and their structures have been elucidated by 1D and 2D NMR ((1)H, (13)C, DEPT, COSY-45, COSY-RCT, HSQC, HMBC, and NOESY spectra) and MALDI-TOF mass spectrometry. Mycalosides B (2) and C (3) were shown to be 27- and 28-nor derivatives of the previously known tetraoside mycaloside A (1). Mycaloside D (4) differs from 1 only in the presence of an additional acetyl group in the carbohydrate moiety. Mycaloside E (5) was structurally identified as a 28-nor-4-dehydroxy derivative of 1. Mycalosides F-H (6-8), differing from each other by the structures of their side chains and nonacetylated (7, 8) or acetylated (6) tetrasaccharide carbohydrate moieties, have new 5(6)-unsaturated 3 beta,4 beta,21-trihydroxy-15-keto-steroidal aglycons. Mycaloside I (9) is a tetraoside of a new 7,24(28)-diunsaturated 3beta,15 beta,29-trihydroxystigmastane aglycon. It was established that the total fraction of the mycalosides as well as mycalosides A (1) and G (7) inhibit the fertilization of eggs by sperm of the sea urchin Strongylocentrotus nudus preincubated with these compounds.
从加勒比海绵Mycale laxissima的极性提取物中分离出了新的甾体寡糖苷麦卡洛苷B - I（2 - 9），并通过一维和二维核磁共振（（1）H、（13）C、DEPT、COSY - 45、COSY - RCT、HSQC、HMBC和NOESY谱）以及基质辅助激光解吸电离飞行时间质谱对其结构进行了阐明。麦卡洛苷B（2）和C（3）被证明是先前已知的四糖苷麦卡洛苷A（1）的27 - 和28 - 降衍生物。麦卡洛苷D（4）与1的不同之处仅在于碳水化合物部分存在一个额外的乙酰基。麦卡洛苷E（5）在结构上被鉴定为1的28 - 降 - 4 - 脱羟基衍生物。麦卡洛苷F - H（6 - 8）彼此的侧链结构以及非乙酰化（7, 8）或乙酰化（6）的四糖碳水化合物部分不同，具有新的5（6）- 不饱和3β，4β，21 - 三羟基 - 15 - 酮甾体苷元。麦卡洛苷I（9）是一种新的7,24（28）- 二不饱和3β，15β，29 - 三羟基豆甾烷苷元的四糖苷。已确定麦卡洛苷的总馏分以及麦卡洛苷A（1）和G（7）可抑制用这些化合物预孵育的海胆Strongylocentrotus nudus精子对卵子的受精作用。
