Volume 42, Issue 24 pp. 3248-3254
Concise Report

Cobalt-Catalyzed Regioselective Methylative Coupling of Internal Alkynes with Aldehydes/Aldimines

Jiwu Zhang

Jiwu Zhang

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032 China

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Zhikun Liang

Zhikun Liang

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032 China

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Qinglei Chong

Corresponding Author

Qinglei Chong

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032 China

E-mail: [email protected]; [email protected]Search for more papers by this author
Fanke Meng

Corresponding Author

Fanke Meng

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032 China

School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, 1 Sub-lane Xiangshan, Hangzhou, Zhejiang, 310024 China

Beijing National Laboratory for Molecular Sciences, Beijing, 100871 China

E-mail: [email protected]; [email protected]Search for more papers by this author
First published: 24 August 2024

Comprehensive Summary

Catalytic methylative coupling of internal alkynes and aldehydes/aldimines through regioselective oxidative cyclization promoted by a phosphine–Co complex is presented. Such process constitutes an unprecedented and unique approach for Co-catalyzed generation of metallacycles that reversed inherent regiochemical biases to furnish a wide range of allylic alcohols and allylic amides bearing a tetrasubstituted alkene in up to 98% yield with high regioselectivity, representing a novel and general strategy for reversal of substrate-controlled regioselectivity in metal-catalyzed oxidative cyclization.

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