Copper‐Catalyzed Oxidative C(sp3)−H/N−H Cross‐Coupling of Hydrocarbons with P(O)−NH Compounds: the Accelerating Effect Induced by Carboxylic Acid Coproduct

Abstract An chelation‐assisted oxidative C( sp 3 )−H/N−H cross coupling of hydrocarbons with P(O)−NH compounds using copper acetate as catalyst is described. The results of kinetic experiments, mechanistic studies and DFT calculations demonstrate the importance of acetic acid coproduct as an additive for promoting the formation of intermediate bis((diphenylphosphoryl)(quinolin‐8‐yl)amino)copper ( 6 ), and consequently accelerating the construction of C( sp 3 )−N bond. The reaction proceeded efficiently with a wide array of hydrocarbons and P(O)−NH compounds, and the rate acceleration induced by the acetic acid coproduct have been repeatedly proven. Furthermore, the efficiency of small‐scale reaction could be retained upon gram‐scale synthesis in a continuous manner. magnified image