Concurrent Formation of N–H Imines and Carbonyl Compounds by Ruthenium-Catalyzed C–C Bond Cleavage of β-Hydroxy Azides

A commercial cyclopentadienylrutenium dicarbonyl dimer ([CpRu(CO)2]2) efficiently catalyzes the formation of N–H imines and carbonyl compounds simultaneously from β-hydroxy azides via C–C bond cleavage under visible light. Density functional theory calculations for the cleavage reaction support the mechanism involving chelation of alkoxy azide species and liberation of nitrogen as the driving force. The synthetic utility of the reaction was demonstrated by a new amine synthesis promoted by chemoselective allylation of imine and synthesis of isoquinoline.