Rh-Catalyzed Direct Amination of Unactivated C(sp3)−H bond with Anthranils Under Mild Conditions

C−N Bond formation is of great significance due to the ubiquity of nitrogen‐containing compounds. Here, a mild and efficient RhIII‐catalyzed C(sp3)−H aryl amination reaction is reported. Anthranil is employed as the nitrogen source with 100 % atom efficiency. This C−H amination reaction exhibits broad substrate scope without using any external oxidants. Mechanistic studies including rhodacycle intermediates, H–D exchange, kinetic isotope effect (KIE) experiments, and in situ IR are presented. New aminations: A mild and efficient RhIII‐catalyzed C(sp3)−H aryl amination reaction with anthranils, as a new type of amination reagent, was disclosed that performs with 100 % atom efficiency. This protocol does not need any external oxidants and provides a useful method for the construction of synthetically relevant ortho‐aminocarbonyl skeletons.