Identifying key intermediates generated in situ from Cu(II) salt–catalyzed C–H functionalization of aromatic amines under illumination

Copper compounds involved in photocatalysis have recently spurred considerable interest for their novel transformations. However, mechanistic investigations are still in infancy. We find a new type of reaction, that is, Cu(II) salt–catalyzed C–H functionalization of aromatic amines triggered by visible light irradiation. An array of mechanistic observations, including high-resolution mass spectrometry, ultraviolet-visible absorption spectrum, electron spin resonance, x-ray absorption near-edge structure, and density functional theory calculation, have identified the key intermediates generated in situ in the transformation. Integration of single-electron transfer, singlet oxygen ((1)O(2)), and new absorption species, intermediate I and intermediate II formed in situ from Cu(II) salts and substrate amines or imines, respectively, is responsible for the N–H and C–H bond activation of secondary amines to couple with nucleophiles in air, thereby leading to the formation of quinoline, indolo[3,2-c]quinoline, β-amino acid, and 1,4-dihydropyridine derivatives in moderate to good yields under visible light irradiation at room temperature.