Photoinduced Copper‐Catalyzed Asymmetric Three‐Component Radical 1,2‐Azidooxygenation of 1,3‐Dienes

Abstract Radical‐involved multicomponent difunctionalization of 1,3‐dienes has recently emerged as a promising strategy for rapid synthesis of valuable allylic compounds in one‐pot operation. However, the expansion of radical scope and enantiocontrol remain two major challenges. Herein, we describe an unprecedented photoinduced copper‐catalyzed highly enantioselective three‐component radical 1,2‐azidooxygenation of 1,3‐dienes with readily available azidobenziodazolone reagent and carboxylic acids. This mild protocol exhibits a broad substrate scope, high functional group tolerance, and exceptional control over chemo‐, regio‐ and enantioselectivity, providing practical access to diverse valuable azidated chiral allylic esters. Mechanistic studies imply that the chiral copper complex is implicated as a bifunctional catalyst in both the photoredox catalyzed azidyl radical generation and enantioselective radical C−O cross‐coupling.