Transition-metal catalyzed amination of aryl halides has become a useful alternative to classic methods for the synthesis of arylamines. However, the majority of these reactions have been conducted with expensive palladium catalysts or less reactive copper catalysts. A few nickel-catalyzed amination reactions have been reported, but the scope of the amines that undergo these transformations are limited to secondary alkylamines and anilines. We recently disclosed a single-component nickel catalyst for the amination of aryl chlorides with primary alkyl amines. However, this precatalyst did not lead to the coupling of aryl halides with ammonia. To address this limitation, we sought to identify a nickel catalyst for the coupling of aryl chlorides with ammonia, which would allow access to primary aryl amines. Herein, the development, applications, and mechanistic studies of the nickel-catalyzed amination of aryl chlorides with ammonia will be presented. The selectivity of these reactions for the formation of primary arylamines over diarylamines is higher than that of the analogous Pd-catalyzed reactions.

Development of first-row transition-metal catalysts for C-N bond forming reactions: Nickel-catalyzed amination of aryl chlorides with ammonia

248th National Meeting (2014)

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