Catalyst-Controlled Strategies to Override the Bond Dissociation Energy-Driven Selectivity of Benzylic C(sp3)–H Insertions

Abstract Catalytic C(sp3)–H insertion reactions of arylalkanes generally proceed at the benzylic position as a consequence of the lower bond dissociation energy (BDE) of the corresponding C–H bond. This account gives a brief overview of recent studies aimed at designing catalyst-controlled amination reactions to go beyond this BDE-driven selectivity. They permit the selective conversion of neutral C–H bonds with a BDE greater than 95 kcal mol–1 for the formation of alkylamines. 1 Introduction 2 Catalyst-Controlled Site-Selective C–H Insertion Reactions 3 Catalyst-Controlled Intermolecular Amination of Nonactivated C–H Bonds of Arylalkanes 4 Conclusion