SUPERSTOLIDE-A - A POTENT CYTOTOXIC MACROLIDE OF A NEW-TYPE FROM THE NEW-CALEDONIAN DEEP-WATER MARINE SPONGE NEOSIPHONIA-SUPERSTES
SUPERSTOLIDE-A - A POTENT CYTOTOXIC MACROLIDE OF A NEW-TYPE FROM THE NEW-CALEDONIAN DEEP-WATER MARINE SPONGE NEOSIPHONIA-SUPERSTES
复制标题
DOI：
10.1021/ja00094a022
复制
发表时间：
1994-07-27
影响因子：
15
通讯作者：
ZAMPELLA, A
中科院分区：
文献类型：
--
作者：
DAURIA, MV;DEBITUS, C;ZAMPELLA, A
从新喀里多尼亚海域采集的深水海绵Neosiphia Superstes中分离到一种具有高度细胞毒性的大环内酯类化合物Superstolide A(1)。通过对内酯1及其开环衍生的甲酯2和3进行广泛的2D核磁共振实验，确定了其总结构。结合核磁共振数据和对2的丙酮分析确定了C22-C26片段的相对立体化学。根据对4应用GLC改进的Horeau方法确定了1的十碱部分的绝对立体结构，而对1和3应用改进的Mosher方法的结果允许我们对C22-C26片段提出22R，23R，24R，25S，26R构型。我们还提出了超硬脂酸酯A(1)的溶液构象，基于分子动力学和力学计算，使用核磁共振衍生的约束条件。
A highly cytotoxic macrolide, superstolide A (1), has been isolated from the deep water marine sponge Neosiphonia superstes, collected off New Caledonia. The gross structure was determined by extensive 2D NMR experiments on the lactone 1 and on its opened-ring-derived methyl esters 2 and 3. The relative stereochemistries of the decaline moiety and of the C22-C26 fragment were determined by a combination of NMR data and acetonide analysis on 2. Absolute stereostructure of the decaline portion of 1 has been determined on the basis of GLC-modified Horeau's methodology applied to 4, whereas the results of the application of the modified Mosher's method to 1 and 3 allowed us to propose for the C22-C26 fragment the 22R, 23R, 24R, 25S, 26R configuration. We also propose the solution conformations of superstolide A (1) based on molecular dynamics and mechanics calculations using NMR-derived constraints.