Visible‐Light‐Driven Organocatalyzed Chemoselective Oxidation of Benzylamines

Accurately controlling chemoselectivity is a challenging goal in the synthesis of important pharmaceuticals, pesticides, and functional materials. In this work, we report the first example of chemoselective oxidation of benzylamine to producing benzonitriles, benzaldehydes, and imines, respectively, through the regulation of reaction solvent and additive under 400 nm light irradiation using Rose Bengal as a photocatalyst. The organic compounds are successfully used as photocatalysts for the first time in the oxidative cyanation of benzylamine in photocatalytic systems. Control experiments, mechanism studies, and density functional theory calculations revealed that the reaction undergoes a photolytical single‐electron transfer process, and the cleavage of the benzylic CH bond is the rate‐determining step in the reaction. Noted that the active species of Rose Bengal‐acetamidine hydrochloride was found and structurally verified by X‐ray single‐crystal diffraction analysis.