Catalyst‐Free Photooxidative Benzylic CH Azolation

Photoredox‐catalyzed hydrogen atom transfer (HAT) and radical–polar crossover (RPC) have emerged as a powerful strategy for the C(sp 3 )–H functionalization of organic molecules. Herein, we disclose a transition metal‐ and photocatalyst‐free photooxidative azolation of C(sp 3 )–H bonds with azoles using CBr 4 . This amination performed at room temperature under 400–405 nm irradiation was operationally simple, and tolerated a variety of functional groups. Its utility in synthesis was demonstrated by the late‐stage functionalization of a drug molecule. CBr 4 acted as a HAT agent and oxidant, undergoing photochemical homolysis to promote this cross‐dehydrogenative coupling reaction.