Two-dimensional NMR analysis of acetonide derivatives in the stereochemical assignment of polyol chains: The absolute configurations of dermostatins A and B
Two-dimensional NMR analysis of acetonide derivatives in the stereochemical assignment of polyol chains: The absolute configurations of dermostatins A and B
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DOI：
10.1021/jo970213f
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发表时间：
1997-05-02
影响因子：
3.6
通讯作者：
Rogers, BN
中科院分区：
文献类型：
--
作者：
Rychnovsky, SD;Richardson, TI;Rogers, BN
我们报道了一种新的、集成的方法，用于指定1，3-跳过的多元醇链的构型，并以皮抑素A和B的构型指定为例说明了该方法。该方法是围绕C-13丙酮分析设计的，它允许人们可靠地确定分离的1，3-二醇的相对立体化学，并使用DQF-COSY、HMQC和ROESY实验进行扩展，这些实验允许聚丙酮衍生物的每个丙酮被明确地指定为syn或anti。利用这一策略，仅使用两个聚丙酮衍生物就确定了皮抑素A C13-C32多元醇链的相对构型。皮抑素A的绝对构型为15S，16S，17R，19R，21R，23S，25S，27R，29R，31R，34S，35S，，皮抑素B的绝对构型为15S，16S，17R，19R，21R，23S，25S，27R，29R，31R，34S，35S，36S.二维C-13丙酮分析为交替多元醇链的立体化学指认提供了一种强有力的新工具。
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.