Reactivity in Nickel‐Catalyzed Multi‐component Sequential Reductive Cross‐Coupling Reactions

The nickel-catalyzed three-component reductive carbonylation of alkyl halides, aryl halides, and ethyl chloroformate is described. Ethyl chloroformate is utilized as a safe and readily available source of CO in this multi-component protocol, providing an efficient and practical alternative for the synthesis of aryl-alkyl ketones. The reaction exhibits a wide substrate scope and good functional group compatibility. Experimental and DFT mechanistic studies highlight the complexity of the cross-electrophile coupling and provide insight into the sequence of the three consecutive oxidative additions of aryl halide, chloroformate, and alkyl halide.