Nickel-Catalyzed Enantioconvergent Transformation of Anisole Derivatives via Cleavage of C-OMe Bond

J Am Chem Soc. 2023 Jul 26;145(29):15721-15728. doi: 10.1021/jacs.3c05845. Epub 2023 Jul 11.

Abstract

Herein, a protocol for enantioconvergent transformation of anisole derivatives is disclosed via nickel-catalyzed dynamic kinetic asymmetric cross-coupling of the C(Ar)-OMe bond. Versatile axially chiral heterobiaryls are successfully assembled. Synthetic transformations demonstrate the application potential of this method. Mechanistic studies indicate that the enantioconvergence of this transformation might be accessed through a chiral ligand-controlled epimerization of diastereomeric 5-membered aza-nickelacycle species rather than a conventional dynamic kinetic resolution.