用于多元醇链立体化学归属的丙酮化物衍生物的二维核磁共振分析：抑皮素A和B的绝对构型

Two-Dimensional NMR Analysis of Acetonide Derivatives in the Stereochemical Assignment of Polyol Chains: The Absolute Configurations of Dermostatins A and B.

作者信息

Rychnovsky Scott D., Richardson Timothy I., Rogers Bruce N.

机构信息

Departments of Chemistry, University of California, Irvine, California 92697-2025, and University of Minnesota, Minneapolis, Minnesota 55455-0431.

出版信息

J Org Chem. 1997 May 2;62(9):2925-2934. doi: 10.1021/jo970213f.

DOI:10.1021/jo970213f

PMID:11671656

Abstract

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 (13)C 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 (13)C acetonide analysis is a very powerful new tool for the stereochemical assignment of alternating polyol chains.

摘要

我们报道了一种用于确定1,3-间隔多元醇链构型的全新综合策略，并通过对抑皮素A和B的构型确定来说明该方法。该方法围绕着(13)C缩酮分析设计，它能让人可靠地确定分离出的1,3-二醇的相对立体化学，并且通过DQF-COSY、HMQC和ROESY实验进行扩展，这些实验能明确地将聚缩酮衍生物的每个缩酮指定为顺式或反式。使用该策略，仅用两种聚缩酮衍生物就确定了抑皮素A中C13 - C32多元醇链的相对构型。抑皮素A的绝对构型为15S,16S,17R,19R,21R,23S,25S,27R,29R,31R,34S,35S，抑皮素B的构型为15S,16S,17R,19R,21R,23S,25S,27R,29R,31R,34S,35S,36S。二维(13)C缩酮分析是用于交替多元醇链立体化学确定的一种非常强大的新工具。