Nickel‐Catalyzed Cross‐Coupling of Sulfonamides With (Hetero)aryl Chlorides

Abstract The development of Ni‐catalyzed C−N cross‐couplings of sulfonamides with (hetero)aryl chlorides is reported. These transformations, which were previously achievable only with Pd catalysis, are enabled by use of air‐stable ( L )NiCl( o ‐tol) pre‐catalysts (L= PhPAd‐DalPhos and PAd2‐DalPhos ), without photocatalysis. The collective scope of (pseudo)halide electrophiles (X=Cl, Br, I, OTs, and OC(O)NEt 2 ) demonstrated herein is unprecedented for any reported catalyst system for sulfonamide C−N cross‐coupling (Pd, Cu, Ni, or other). Preliminary competition experiments and relevant coordination chemistry studies are also presented.