Enantioselective reductive cross-couplings to forge C(sp<sup>2</sup>)-C(sp<sup>3</sup>) bonds by merging electrochemistry with nickel catalysis.

Wang, Yun-Zhao; Sun, Bing; Guo, Jian-Feng; Zhu, Xiao-Yu; Gu, Yu-Cheng; Han, Ya-Ping; Ma, Cong; Mei, Tian-Sheng · Nat Commun · 2025

basic_science · Level V

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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<sup>I</sup> species activate aryl halides via oxidative addition and alkyl chlorides via single electron transfer.