Nickel/Iridium Metallaphotoredox Catalysis for Allylic C–H Bond Arylation of <i>N</i>-Allyl Heterocycles

Despite conceptual breakthroughs in dual photoredox- and nickel-catalyzed arylation of radicals, the approach remains largely limited to localized C-centered radicals. Here, we extend it to allylic radicals, focusing on <i>N</i>-allyl heterocycles. Using [Ir(dF(CF₃)ppy)₂(dtbbpy)]PF₆ and NiCl₂(dtbbpy) under visible light, we achieve regioselective γ-amino radical arylation, yielding enamines in good yields. In some cases, in situ photoisomerization produces the <i>Z</i> isomer, influenced by the substrate and the triplet state energy of the photocatalyst.