Asymmetric Synthesis of Sulfur-Containing Quaternary Stereocenters via Dual Nickel/Photoredox Synergistic Catalysis

Organosulfur motifs are privileged scaffolds in bioactive molecules and pharmaceutical synthesis, yet the enantioselective construction of sulfur-bearing quaternary stereogenic centers remains a formidable challenge. Herein, we report a visible-light-mediated nickel/photoredox dual catalytic asymmetric allylation of sulfur-substituted allylic esters with aldehydes, delivering homoallylic alcohols with vicinal stereocenters and excellent stereoselectivity. Mechanistic studies confirm the light-induced Z/E interconversion of allylic ester substrates. Strikingly, the two geometric isomers exhibit an enormous kinetic gap in the reaction: the Z isomer displays superior reactivity and thus dominates the productive catalytic pathway, representing a distinctive geometry-controlled kinetic discrimination effect.