Photoredox/Nickel‐Catalyzed Single‐Electron Tsuji–Trost Reaction: Development and Mechanistic Insights

A regioselective, nickel-catalyzed photoredox allylation of secondary, benzyl, and α-alkoxy radical precursors is disclosed. Through this manifold, a variety of linear allylic alcohols and allylated monosaccharides are accessible in high yields under mild reaction conditions. Quantum mechanical calculations [DFT and DLPNO-CCSD(T)] support the mechanistic hypothesis of a Ni⁰ to Ni^II oxidative addition pathway followed by radical addition and inner-sphere allylation.