10.1021/acscatal.9b03715.s001 Ryan T. McGuire Ryan T. McGuire Julia F. J. Paffile Julia F. J. Paffile Yuqiao Zhou Yuqiao Zhou Mark Stradiotto Mark Stradiotto Nickel-Catalyzed C–N Cross-Coupling of Ammonia, (Hetero)anilines, and Indoles with Activated (Hetero)aryl Chlorides Enabled by Ligand Design American Chemical Society 2019 Hetero Ni hetero reactivity C 1 chloride cross-coupling PAd 2-DalPhos precatalyst C 4 2019-09-16 12:34:28 Dataset https://acs.figshare.com/articles/dataset/Nickel-Catalyzed_C_N_Cross-Coupling_of_Ammonia_Hetero_anilines_and_Indoles_with_Activated_Hetero_aryl_Chlorides_Enabled_by_Ligand_Design/9850937 The Ni­(II) precatalyst (<b>C1</b>) featuring the phosphonite ancillary ligand Phen-DalPhos (<b>L1</b>) 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 <b>C4</b> 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 <b>C1</b> and <b>C4</b> from other metal catalysts (i.e., copper, palladium, nickel, or other) within the field of C–N cross-coupling chemistry.