Salicylic acid complexed with TiO2 for visible light-driven selective oxidation of amines into imines with air

摘要

The interplay of salicylic acid (SA) and reactive oxygen species (ROS) can modulate biotic and abiotic stress of plants, essential biological aerobic oxidation processes. Meanwhile, ROS plays a critical role in TiO2 photo catalytic system for the degradation of organic species. Herein, we developed a system consisted of SA and TiO2 aiming at the selective oxidation of organic molecules by ROS. Interestingly, SA complexed with TiO2 leads to ligand-to-metal charge transfer (LMCT) under visible light irradiation. The charge transfer from ligand (chemically adsorbed SA) to metal (conduction band of TiO2) activates O-2 to ROS, superoxide (O-2(center dot-)). The positive charge located at ligand SA is connected with (2,2,6,6-tetramethylpiperidin-l-yl)oxyl (TEMPO) catalysis for direct two-electron oxidation of amines and later regenerated by O-2(center dot-) SA and its derivatives were screened as ligands of TiO2 for the selective aerobic oxidation of amines into imines under blue light-emitting diode (LED) irradiation in which 5-CH3O-SA (5-methoxysalicylic acid, 0.8 mol%) complexed with anatase TiO2 and coupled with TEMPO (5 mol%) confers significantly better results than the others. By this visible light LMCT route, both primary amines and secondary amines can be selectively oxidized into corresponding imines with atmosphere O-2 as the terminal oxidant. Importantly, the desired product of N-benzylidenebenzylamine can be isolated in 92% yield.