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通过短寿命中间体进行的催化光化学消旋化

Catalytic Photochemical Deracemization via Short-Lived Intermediates.

作者信息

Großkopf Johannes, Bach Thorsten

机构信息

School of Natural Sciences, Technische Universität München, Department Chemie and Catalysis Research Center (CRC), Lichtenbergstr. 4, 85747, Garching, Germany.

出版信息

Angew Chem Int Ed Engl. 2023 Dec 11;62(50):e202308241. doi: 10.1002/anie.202308241. Epub 2023 Sep 19.

Abstract

Upon irradiation in the presence of a suitable chiral catalyst, racemic compound mixtures can be converted into enantiomerically pure compounds with the same constitution. The process is called photochemical deracemization and involves the formation of short-lived intermediates. By opening different reaction channels for the forward reaction to the intermediate and for the re-constitution of the chiral molecule, the entropically disfavored process becomes feasible. Since the discovery of the first photochemical deracemization in 2018, the field has been growing rapidly. This review comprehensively covers the research performed in the area and discusses current developments. It is subdivided according to the mode of action and the respective substrate classes. The focus of this review is on the scope of the individual reactions and on a discussion of the mechanistic details underlying the presented reaction.

摘要

在合适的手性催化剂存在下进行辐照时,外消旋化合物混合物可转化为具有相同组成的对映体纯化合物。该过程称为光化学消旋化,涉及短寿命中间体的形成。通过为中间体的正向反应和手性分子的重新构建打开不同的反应通道,熵不利的过程变得可行。自2018年首次发现光化学消旋化以来,该领域一直在迅速发展。本综述全面涵盖了该领域的研究,并讨论了当前的进展。它根据作用方式和相应的底物类别进行细分。本综述的重点是各个反应的范围以及对所呈现反应背后的机理细节的讨论。

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