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铜/ TEMPO催化叔环胺通过肖诺型氧化实现对映选择性C(sp³)-H炔基化反应

Cu /TEMPO-Catalyzed Enantioselective C(sp )-H Alkynylation of Tertiary Cyclic Amines through Shono-Type Oxidation.

作者信息

Gao Pei-Sen, Weng Xin-Jun, Wang Zhen-Hua, Zheng Chao, Sun Bing, Chen Zhi-Hao, You Shu-Li, Mei Tian-Sheng

机构信息

State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Science, 345 Lingling Road, Shanghai, 200032, China.

出版信息

Angew Chem Int Ed Engl. 2020 Aug 24;59(35):15254-15259. doi: 10.1002/anie.202005099. Epub 2020 Jun 15.

DOI:10.1002/anie.202005099
PMID:32394631
Abstract

A novel strategy for asymmetric Shono-type oxidative cross-coupling has been developed by merging copper catalysis and electrochemistry, affording C1-alkynylated tetrahydroisoquinolines with good to excellent enantioselectivity. The use of TEMPO as a co-catalytic redox mediator is crucial not only for oxidizing a tetrahydroisoquinoline to an iminium ion species but also for decreasing the oxidation potential of the reaction. A novel bisoxazoline ligand is also reported.

摘要

通过结合铜催化和电化学,开发了一种用于不对称Shono型氧化交叉偶联的新策略,可提供对映选择性良好至优异的C1-炔基化四氢异喹啉。使用TEMPO作为共催化氧化还原介质不仅对于将四氢异喹啉氧化为亚胺离子物种至关重要,而且对于降低反应的氧化电位也至关重要。还报道了一种新型双恶唑啉配体。

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