Enantioselective Copper-Catalyzed Alkynylation of Benzylic C–H Bonds via Radical Relay
Liang Fu, Zhihan Zhang, Pinhong Chen, Zhenyang Lin, Guosheng Liu
Abstract
The first enantioselective alkynylation of benzylic C–H bonds via copper-catalyzed radical relay has been established herein, which provides an easy access to structurally diverse benzylic alkynes in good yields with excellent enantioselectivities. A key step for the asymmetric copper-catalyzed radical relay process is the enantioselective capture of a benzylic radical with chiral (Box)CuII-alkynyl species. In addition, the reaction displays good functional group tolerance, broad substrate scope, and mild conditions. The enantioenriched alkynylation products can be readily transformed into highly valuable synthons, such as chiral terminal alkynes, allenes, alkenes, and carboxylic acids. More importantly, our methodology can be applied to the synthesis of bioactive molecule AMG 837.