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

Abstract 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.