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柠檬菌素A和B的对映选择性全合成。对其指定结构的立体化学修正。

Enantioselective total syntheses of citrinadins A and B. Stereochemical revision of their assigned structures.

作者信息

Bian Zhiguo, Marvin Christopher C, Pettersson Martin, Martin Stephen F

机构信息

Department of Chemistry, The University of Texas , Austin, Texas 78712, United States.

出版信息

J Am Chem Soc. 2014 Oct 8;136(40):14184-92. doi: 10.1021/ja5074646. Epub 2014 Sep 29.

DOI:10.1021/ja5074646
PMID:25211501
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC4195386/
Abstract

The concise, enantioselective total syntheses of (-)-citrinadin A and (+)-citrinadin B in a total of only 20 and 21 steps, respectively, from commercially available starting materials are described. Our strategy, which minimizes refunctionalization and protection/deprotection operations, features the highly diastereoselective, vinylogous Mannich addition of a dienolate to a chiral pyridinium salt to set the first chiral center. The absolute stereochemistry of this key center was then relayed by a sequence of substrate-controlled reactions, including a highly stereoselective epoxidation/ring opening sequence and an oxidative rearrangement of an indole to furnish a spirooxindole to establish the remaining stereocenters in the pentacyclic core of the citrinadins. An early stage intermediate in the synthesis of (-)-citrinadin A was deoxygenated to generate a dehydroxy compound that was elaborated into (+)-citrinadin B by a sequence of reaction identical to those used to prepare (-)-citrinadin A. These concise syntheses of (-)-citrinadin A and (+)-citrinadin B led to a revision of their stereochemical structures.

摘要

本文描述了分别以市售起始原料，仅通过20步和21步的简洁对映选择性全合成方法，合成（-）-柑橘霉素A和（+）-柑橘霉素B。我们的策略是尽量减少重新官能团化和保护/脱保护操作，其特点是将烯醇化物高度非对映选择性地、乙烯型曼尼希加成到手性吡啶盐上，以构建第一个手性中心。然后通过一系列底物控制的反应传递该关键中心的绝对立体化学，包括高度立体选择性的环氧化/开环序列以及吲哚的氧化重排，以提供一个螺环氧化吲哚，从而在柑橘霉素的五环核心中建立其余的立体中心。在合成（-）-柑橘霉素A的早期中间体被脱氧生成一种脱羟基化合物，该化合物通过与制备（-）-柑橘霉素A相同的一系列反应转化为（+）-柑橘霉素B。（-）-柑橘霉素A和（+）-柑橘霉素B的这些简洁合成导致了它们立体化学结构的修正。

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