Photochemical C4-Selective C-H Amination of Quinolines via N-Shift of Heteroaryl Azides

Access to 3,4-diaminoazines is limited by regioselectivity challenges in azine functionalization. We report a photochemical strategy enabling the direct synthesis of 3,4-diaminoazines through C3-to-C4 nitrogen migration (N-shift). Blue LED irradiation of 3-azidoquinolines at room temperature allows C4-selective C-H amination while concurrently installing diverse amines at the C3-position. In contrast, N-shifts in 3-azidopyridines preferentially form diazepines, reflecting divergent reactivity governed by N-heterocycle electronics, as supported by computational analysis.