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Catalytic Asymmetric Electrochemical α‐Arylation of Cyclic β‐Ketocarbonyls with Anodic Benzyne Intermediates
Author(s) -
Li Longji,
Li Yao,
Fu Niankai,
Zhang Long,
Luo Sanzhong
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202006016
Subject(s) - aryne , enamine , stereocenter , chemistry , catalysis , combinatorial chemistry , computational chemistry , organic chemistry , enantioselective synthesis
Asymmetric catalysis with benzyne remains elusive because of the highly fleeting and nonpolar nature of benzyne intermediates. Reported herein is an electrochemical approach for the oxidative generation of benzynes (cyclohexyne) and its successful merging with chiral primary aminocatalysis, formulating the first catalytic asymmetric enamine–benzyne (cyclohexyne) coupling reaction. Cobalt acetate was identified to stabilize the in situ generated arynes and facilitate its coupling with an enamine. This catalytic enamine‐benzyne protocol provides a concise method for the construction of diverse α‐aryl (α‐cyclohexenyl) quaternary carbon stereogenic centers with good stereoselectivities.