Enantioselective reductive cross-couplings to forge C(sp2)–C(sp3) bonds by merging electrochemistry with nickel catalysis

Abstract

Motivated by the inherent benefits of synergistically combining electrochemical methodologies with nickel catalysis, we present here a Ni-catalyzed enantioselective electroreductive cross-coupling of benzyl chlorides with aryl halides, yielding chiral 1,1-diaryl compounds with good to excellent enantioselectivity. This catalytic reaction can not only be applied to aryl chlorides/bromides, which are challenging to access by other means, but also to benzyl chlorides containing silicon groups. Additionally, the absence of a sacrificial anode lays a foundation for scalability. The combination of cyclic voltammetry analysis with electrode potential studies suggests that Ni^I species activate aryl halides via oxidative addition and alkyl chlorides via single electron transfer.