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光氧化还原与镍双催化实现环丙醇的不对称β-芳基化反应。

Asymmetric β-arylation of cyclopropanols enabled by photoredox and nickel dual catalysis.

作者信息

Wang Jianhua, Li Xiaoxun

机构信息

Department of Medicinal Chemistry, Key Laboratory of Chemical Biology (Ministry of Education), NMPA Key Laboratory for Technology Research and Evaluation of Drug Products, School of Pharmaceutical Sciences, Cheeloo College of Medicine, Shandong University Jinan Shandong 250012 China

出版信息

Chem Sci. 2022 Feb 17;13(10):3020-3026. doi: 10.1039/d1sc07237d. eCollection 2022 Mar 9.

Abstract

The enantioselective functionalization and transformation of readily available cyclopropyl compounds are synthetically appealing yet challenging topics in organic synthesis. Here we report an asymmetric β-arylation of cyclopropanols with aryl bromides enabled by photoredox and nickel dual catalysis. This dual catalytic transformation features a broad substrate scope and good functional group tolerance at room temperature, providing facile access to a wide array of enantioenriched β-aryl ketones bearing a primary alcohol moiety in good yields with satisfactory enantioselectivities (39 examples, up to 83% yield and 90% ee). The synthetic value of this protocol was illustrated by the concise asymmetric construction of natural product calyxolane B analogues.

摘要

在手性有机合成中,易于获得的环丙基化合物的对映选择性官能团化和转化是具有合成吸引力但具有挑战性的课题。在此,我们报道了一种通过光氧化还原和镍双催化实现的环丙醇与芳基溴的不对称β-芳基化反应。这种双催化转化具有广泛的底物范围,并且在室温下对官能团具有良好的耐受性,能够方便地获得一系列带有伯醇部分的对映体富集的β-芳基酮,产率良好,对映选择性令人满意(39个例子,产率高达83%,对映体过量值高达90%)。天然产物萼烷醇B类似物的简洁不对称构建说明了该方法的合成价值。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/84b4/8905987/be011e393037/d1sc07237d-s1.jpg

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