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后期诱导和富集阻转异构体手性的立体动力学策略。

Stereodynamic Strategies to Induce and Enrich Chirality of Atropisomers at a Late Stage.

作者信息

Roos Casey B, Chiang Chang-Hwa, Murray Lauren A M, Yang Di, Schulert Luke, Narayan Alison R H

出版信息

Chem Rev. 2023 Sep 13;123(17):10641-10727. doi: 10.1021/acs.chemrev.3c00327. Epub 2023 Aug 28.

Abstract

Enantiomers, where chirality arises from restricted rotation around a single bond, are atropisomers. Due to the unique nature of the origins of their chirality, synthetic strategies to access these compounds in an enantioselective manner differ from those used to prepare enantioenriched compounds containing point chirality arising from an unsymmetrically substituted carbon center. In particular stereodynamic transformations, such as dynamic kinetic resolutions, thermodynamic dynamic resolutions, and deracemizations, which rely on the ability to racemize or interconvert enantiomers, are a promising set of transformations to prepare optically pure compounds in the late stage of a synthetic sequence. Translation of these synthetic approaches from compounds with point chirality to atropisomers requires an expanded toolbox for epimerization/racemization and provides an opportunity to develop a new conceptual framework for the enantioselective synthesis of these compounds.

摘要

手性源于围绕单键的受限旋转的对映体是阻转异构体。由于其手性起源的独特性质,以对映选择性方式获得这些化合物的合成策略不同于用于制备含有由不对称取代的碳中心产生的点手性的对映体富集化合物的策略。特别是立体动力学转化,如动态动力学拆分、热力学动态拆分和外消旋化,它们依赖于对映体的外消旋化或相互转化能力,是在合成序列后期制备光学纯化合物的一组有前景的转化方法。将这些合成方法从具有点手性的化合物转化为阻转异构体需要一个用于差向异构化/外消旋化的扩展工具箱,并为开发这些化合物的对映选择性合成的新概念框架提供了机会。

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