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镍催化的对映选择性还原共轭芳基化和杂芳基化:通过 1,4-加成的基本反应机制。

Nickel-Catalyzed Enantioselective Reductive Conjugate Arylation and Heteroarylation via an Elementary Mechanism of 1,4-Addition.

机构信息

State Key Laboratory of Chemical Oncogenomics, Guangdong Provincial Key Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Room F312, 2199 Lishui Road, Nanshan District, Shenzhen 518055, China.

School of Chemistry, Chemical Engineering and Biotechnology, Nanyang Technological University, 21 Nanyang Link, 637371, Singapore.

出版信息

J Am Chem Soc. 2022 Nov 9;144(44):20249-20257. doi: 10.1021/jacs.2c05678. Epub 2022 Oct 31.

DOI:10.1021/jacs.2c05678
PMID:36315074
Abstract

A nickel complex of isoquinox promoted enantioselective conjugate arylation and heteroarylation of enones using aryl and heteroaryl halides directly. The reaction was successfully applied to stereoselective syntheses of -turmerone, chiral fragments of (+)-tolterodine and AZD5672. Mechanistically, experiments and calculations supported that an arylnickel(I) complex inserted to enones via an elementary 1,4-addition.

摘要

一种异喹啉酮镍配合物促进了烯酮的对映选择性共轭芳基化和杂芳基化反应,可直接使用芳基和杂芳基卤化物。该反应成功应用于 β-姜黄烯酮、(+)-托特罗定和 AZD5672 手性片段的立体选择性合成。在机理上,实验和计算都支持芳基镍(I)配合物通过基本的 1,4-加成插入到烯酮中。

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