Nickel-Catalyzed C–N Cross-Coupling of Ammonia, (Hetero)anilines, and Indoles with Activated (Hetero)aryl Chlorides Enabled by Ligand Design

The Ni­(II) precatalyst (C1) featuring the phosphonite ancillary ligand Phen-DalPhos (L1) was employed in the cross-coupling of (hetero)­anilines with (hetero)­aryl chlorides and in the diarylation of ammonia with (hetero)­aryl chlorides to afford heteroatom-dense di­(hetero)­arylamines. The PAd2-DalPhos precatalyst C4 provided complementary reactivity in cross-couplings of indoles with (hetero)­aryl chlorides. Taken together, the demonstration of room-temperature reactivity within each of the reaction classes examined and the observation of useful chemoselectivity at low loading (≤0.5 mol % Ni) and on gram-scale distinguishes C1 and C4 from other metal catalysts (i.e., copper, palladium, nickel, or other) within the field of C–N cross-coupling chemistry.