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Copper(I)‐Catalyzed Asymmetric Conjugate 1,6‐, 1,8‐, and 1,10‐Borylation
Author(s) -
Shi ChangYun,
Eun Jungmin,
Newhouse Timothy R.,
Yin Liang
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202016081
Subject(s) - borylation , regioselectivity , conjugate , chemistry , electrophile , enantioselective synthesis , catalysis , combinatorial chemistry , organic chemistry , mathematics , aryl , mathematical analysis , alkyl
Catalytic asymmetric remote conjugate borylation is challenging as the control of regioselectivity is not trivial, the electrophilicity of remote sites is extenuated, and the remote asymmetric induction away from the carbonyl group is difficult. Herein, catalytic asymmetric conjugate 1,6‐, 1,8‐ and 1,10‐borylation was developed with excellent regioselectivity, which delivered α‐chiral boronates in moderate to high yields with high enantioselectivity. The produced chiral boronate smoothly underwent oxidation, cross‐coupling, and one‐carbon homologation to give synthetically versatile chiral compounds in moderate yields with excellent stereoretention. Furthermore, a stereomechanistic analysis was conducted using DFT calculations, which provides insights into the origins of the regioselectivity. Finally, the present 1,6‐borylation was successfully applied in an efficient one‐pot asymmetric synthesis of (−)‐7,8‐dihydrokavain.