Chemoselective Transfer Hydrogenation of Nitroarenes with Ammonia Borane Catalyzed by Copper N‐heterocyclic Carbene Complexes

Comprehensive Summary Herein, we present a method for the homogeneous hydrogenation of nitroarenes to produce anilines using low catalyst loading (1 mo%) of copper N ‐heterocyclic carbene complexes as the catalyst and ammonia borane as the source of hydrogen. A wide range of nitroarenes, featuring diverse functional groups, were selectively transformed into their corresponding primary aromatic amines with high yields. This process can be readily scaled up and exhibits compatibility with various sensitive functional groups, including halogen, trifluoromethyl, aminomethyl, alkenyl, cyano, ester, amide, and hydroxyl. Notably, this catalytic methodology finds application in the synthesis of essential drug compounds. Mechanistic investigations suggest that the in‐situ ‐generated Cu‐H species may serve as active intermediates, with reduction pathways involving species such as azobenzene, 1,2‐diphenylhydrazine, nitrosobenzene, and N ‐phenylhydroxylamine.