Understanding Formation and Roles of Ni^II Aryl Amido and Ni^III Aryl Amido Intermediates in Ni-Catalyzed Electrochemical Aryl Amination Reactions.

ABSTRACT: Ni-catalyzed electrochemical aryl amination (e-amination) is an attractive, emerging approach to building C-N bonds. Here, we report in-depth experimental and computational studies that examined the mechanism of Ni-catalyzed e-amination reactions. Key Ni^II-amine dibromide and Ni^II aryl amido intermediates were chemically synthesized and characterized. The combination of experiments and DFT calculations suggest (1) there is coordination of an amine to the Ni^II catalyst before the cathodic reduction and oxidative addition steps, (2) a stable Ni^II aryl amido intermediate is produced from the cathodic half-reaction, a critical step in controlling the selectivity between cross-coupling and undesired homo-coupling reaction pathways, (3) the diazabicycl

SUBMITTER: Luo J 

PROVIDER: S-EPMC10635587 | biostudies-literature | 2023 Jul

REPOSITORIES: biostudies-literature