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可见光促进的手性自由基转化反应。

Catalytic Enantioselective Radical Transformations Enabled by Visible Light.

机构信息

Department of Chemistry, Krishnagar Govt. College, Krishnagar, Nadia, 741101, India.

出版信息

Chem Asian J. 2020 Jul 16;15(14):2129-2152. doi: 10.1002/asia.202000525. Epub 2020 Jun 17.

Abstract

Visible light has been recognized as an economical and environmentally benign source of energy that enables chemoselective molecular activation of chemical reactions and hence reveal a new horizon for the design and discovery of novel chemical transformations. On the other hand, asymmetric catalysis represents an economic method to satisfy the increasing need for enantioenriched compounds in the chemical and pharmaceutical industries. Therefore, combining visible light photocatalysis with asymmetric catalysis creates a wider range of opportunities for the development of mechanistically unique reaction schemes. However, there arise two main problems like undesirable photochemical background reactions and difficulties in controlling the stereochemistry with highly reactive photochemical intermediates which can pose a serious challenge to the development of asymmetric visible light photocatalysis. In recent years, several methods have been developed to overcome these challenges. This review summarizes the recent advances in visible light-induced enantioselective reactions. We divide our discussion into four categories: Asymmetric photoredox organocatalysis, asymmetric transition metal photoredox catalysis, asymmetric photoredox Lewis acid catalysis and asymmetric photoinduced energy transfer catalysis. Special emphasis has been given to different catalytic activation modes that enable the construction of challenging carbon-carbon and carbon-heteroatom bond in an enantioselective fashion. A brief analysis of substrate scope and limitation as well as reaction mechanism of these reactions has been included.

摘要

可见光已被公认为一种经济且环境友好的能源,可实现化学反应的化学选择性分子激活,从而为新型化学转化的设计和发现开辟了新的前景。另一方面,不对称催化是满足化学和制药工业对手性化合物日益增长需求的经济方法。因此,将可见光光催化与不对称催化相结合,为开发具有独特机理的反应方案创造了更多机会。然而,存在两个主要问题,例如不希望发生的光化学反应背景反应和难以控制高反应性光化学中间体的立体化学,这对不对称可见光光催化的发展构成了严重挑战。近年来,已经开发出几种方法来克服这些挑战。本综述总结了可见光诱导对映选择性反应的最新进展。我们将讨论分为四类:不对称光氧化还原有机催化、不对称过渡金属光氧化还原催化、不对称光氧化还原路易斯酸催化和不对称光诱导能量转移催化。特别强调了不同的催化激活模式,这些模式能够以对映选择性的方式构建具有挑战性的碳-碳和碳-杂原子键。还包括了这些反应的底物范围和限制以及反应机理的简要分析。

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