Enantioselective Copper-Catalyzed Alkynylation of Benzylic C–H Bonds via Radical Relay
- 15 June 2020
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 142 (28), 12493-12500
- https://doi.org/10.1021/jacs.0c05373
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.Funding Information
- Research Grants Council, University Grants Committee (HKUST 16304416)
- Science and Technology Commission of Shanghai Municipality (17JC1401200, 17XD1404500, 19590750400)
- National Natural Science Foundation of China (21532009, 21790330, 21821002, 91956202)
- Chinese Academy of Sciences (121731KYSB20190016, QYZDJSSW-SLH055, XDB20000000)
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