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光诱导钴催化二醛的去对称化反应以构建轴手性

Photoinduced Cobalt-Catalyzed Desymmetrization of Dialdehydes to Access Axial Chirality.

作者信息

Jiang Hao, He Xiang-Kui, Jiang Xuan, Zhao Wei, Lu Liang-Qiu, Cheng Ying, Xiao Wen-Jing

机构信息

CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan 430079, P. R. China.

Wuhan Institute of Photochemistry and Technology, 7 Bingang North Road, Wuhan 430083, P. R. China.

出版信息

J Am Chem Soc. 2023 Mar 29;145(12):6944-6952. doi: 10.1021/jacs.3c00462. Epub 2023 Mar 15.

Abstract

Enantioselective metallaphotoredox catalysis, which combines photoredox catalysis and asymmetric transition-metal catalysis, has become an effective approach to achieve stereoconvergence under mild conditions. Although many impressive synthetic approaches have been developed to access central chirality, the construction of axial chirality by metallaphotoredox catalysis still remains underexplored. Herein, we report two visible light-induced cobalt-catalyzed asymmetric reductive couplings of biaryl dialdehydes to synthesize axially chiral aldehydes (60 examples, up to 98% yield, >19:1 dr, and >99% ee). This protocol shows good functional group tolerance, broad substrate scope, and excellent diastereo- and enantioselectivity.

摘要

对映选择性金属光氧化还原催化,将光氧化还原催化与不对称过渡金属催化相结合,已成为在温和条件下实现立体收敛的有效方法。尽管已经开发出许多令人印象深刻的合成方法来构建中心手性,但通过金属光氧化还原催化构建轴手性仍未得到充分探索。在此,我们报道了两种可见光诱导的钴催化的联芳基二醛不对称还原偶联反应,用于合成轴手性醛(60个例子,产率高达98%,非对映选择性大于19:1,对映体过量值大于99%)。该方法显示出良好的官能团耐受性、广泛的底物范围以及优异的非对映和对映选择性。

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