Cross-Coupling\nReactions with Nickel, Visible Light,\nand <i>tert</i>-Butylamine as a Bifunctional Additive

Transition metal catalysis is crucial for the synthesis\nof complex\nmolecules, with ligands and bases playing a pivotal role in optimizing\ncross-coupling reactions. Despite advancements in ligand design and\nbase selection, achieving effective synergy between these components\nremains challenging. We present here a general approach to nickel-catalyzed\nphotoredox reactions employing <i>tert</i>-butylamine as\na cost-effective bifunctional additive, acting as the base and ligand.\nThis method proves effective for C–O and C–N bond-forming\nreactions with a diverse array of nucleophiles, including phenols,\naliphatic alcohols, anilines, sulfonamides, sulfoximines, and imines.\nNotably, the protocol demonstrates significant applicability in biomolecule\nderivatization and facilitates sequential one-pot functionalizations.\nSpectroscopic investigations revealed the robustness of the dynamic\ncatalytic system, while elucidation of structure–reactivity\nrelationships demonstrated how computed molecular properties of both\nthe nucleophile and electrophile correlated to reaction performance,\nproviding a foundation for effective reaction outcome prediction.