Wang Yun-Zhao, Sun Bing, Guo Jian-Feng, Zhu Xiao-Yu, Gu Yu-Cheng, Han Ya-Ping, Ma Cong, Mei Tian-Sheng
State Key Laboratory of Organometallic Chemistry, Shanghai of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai, PR China.
Syngenta, Jealott's Hill International Research Centre, Berkshire, UK.
Nat Commun. 2025 Jan 28;16(1):1108. doi: 10.1038/s41467-025-56377-w.
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 species activate aryl halides via oxidative addition and alkyl chlorides via single electron transfer.
受电化学方法与镍催化协同结合的内在优势驱动，我们在此展示了一种镍催化的苄基氯与芳基卤化物的对映选择性电还原交叉偶联反应，可生成对映选择性良好至优异的手性1,1-二芳基化合物。这种催化反应不仅可应用于通过其他方法难以获得的芳基氯/溴化物，还可应用于含硅基团的苄基氯。此外，无需牺牲阳极这一点为反应的规模化应用奠定了基础。循环伏安分析与电极电位研究相结合表明，镍物种通过氧化加成活化芳基卤化物，通过单电子转移活化烷基氯化物。
