Electrophotocatalytic hydrogenation of imines and reductive functionalization of aryl halides

The open-shell catalytically active species, like radical cations or radical anions, generated by one-electron transfer of precatalysts are widely used in energy-consuming redox reactions, but their excited-state lifetimes are usually short. Here, a closed-shell thioxanthone-hydrogen anion species (3), which can be photochemically converted to a potent and long-lived reductant, is generated under electrochemical conditions, enabling the electrophotocatalytic hydrogenation. Notably, TfOH can regulate the redox potential of the active species in this system. In the presence of TfOH, precatalyst (1) reduction can occur at low potential, so that competitive H₂ evolution can be inhibited, thus effectively promoting the hydrogenation of imines. In the absence of TfOH, the reducing ability of the system can reach a potency even comparable to that of Na⁰ or Li⁰, thereby allowing the hydrogenation, borylation, stannylation and (hetero)arylation of aryl halides to construct C-H, C-B, C-Sn, and C-C bonds.