Nickel‐Catalyzed Vinyl C(sp²)‐N Cross‐Electrophile Coupling via Iminyl Radical to Synthesize α‐CF₃‐2‐azadienes

Abstract The development of reactions involving N ‐electrophiles to construct C–N bonds has remained a relatively less explored area in the field of cross‐electrophile coupling. In this study, we present a nickel‐catalyzed cross‐electrophile coupling radical approach that enable vinyl C(sp 2 )─N bond formation, facilitating the synthesis of linear α‐CF₃‐2‐azadienes, which are difficult to obtain via known strategies of C─N bond construction. This approach effectively facilitates the coupling of an iminyl radical with stoichiometric amount of vinyl bromides, demonstrating considerable tolerance to diverse functional groups and exceptional chemoselectivity. Mechanistic investigations demonstrated the generation of an iminyl radical from oxime ester via single‐electron transfer which express comparable reactivity with carbon centered radicals. Moreover, this method could be applied to the late‐stage coupling of various pharmaceuticals.