Two-dimensional NMR analysis of acetonide derivatives in the stereochemical assignment of polyol chains: The absolute configurations of dermostatins A and B

被引：30

作者：

Rychnovsky, SD ^{[1
]}

Richardson, TI ^{[1
]}

Rogers, BN ^{[1
]}

机构：

[1] UNIV MINNESOTA,MINNEAPOLIS,MN 55455

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1997年 / 62卷 / 09期

关键词：

D O I：

10.1021/jo970213f

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

We report a new, integrated strategy for assigning the configuration of 1,3-skipped polyol chains and illustrate the approach with the configurational assignments of both dermostatins A and B. The method is designed around the C-13 acetonide analysis, which allows one to reliably determine the relative stereochemistry of an isolated 1,3-diol and is extended using DQF-COSY, HMQC, and ROESY experiments that allow each acetonide of a polyacetonide derivative to be unambiguously assigned as either syn or anti. Using this strategy, the relative configuration of the dermostatin A C13-C32 polyol chain was determined using just two polyacetonide derivatives. The absolute configuration of dermostatin A is 15S,16S,17R,19R,21R,23S,25S,27R,29R,31R,34S,35S, and the configuration of dermostatin B is 15S,16S,17R,19R,21R,23S,25S,27R,29R,31R,34S,35S,36S. The 2D C-13 acetonide analysis is a very powerful new tool for the stereochemical assignment of alternating polyol chains.

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页码：2925 / 2934

页数：10

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