肌苷糖苷B - I，从海绵宽扁肉芝软珊瑚中分离得到的8种新的精子静止甾体寡糖苷。

Mycalosides B-I, eight new spermostatic steroid oligoglycosides from the sponge Mycale laxissima.

作者信息

Antonov Alexandr S, Afiyatullov Shamil Sh, Kalinovsky Anatoly I, Ponomarenko Ludmila P, Dmitrenok Pavel S, Aminin Dmitry L, Agafonova Irina G, Stonik Valentin A

机构信息

Pacific Institute of Bioorganic Chemistry, Far-Eastern Branch of the Russian Academy of Sciences, Prospect 100 let Vladivostoku, 690022 Vladivostok, Russian Federation.

出版信息

J Nat Prod. 2003 Aug;66(8):1082-8. doi: 10.1021/np0300030.

DOI:10.1021/np0300030

PMID:12932129

Abstract

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.

摘要

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。