Catalytic Enantioselective Construction of Carbon-Sulfur Bonds: Recent Advances and Future Perspectives.

The catalytic enantioselective formation of carbon-sulfur (C-S) bonds is a rapidly evolving field in modern organic synthesis, driven by the importance of chiral sulfur-containing motifs in pharmaceuticals, agrochemicals, and functional materials. Despite their significance, asymmetric C-S bond-forming reactions remain challenging due to the strong coordinating ability and nucleophilicity of sulfur species, catalyst deactivation, and difficulties in controlling sulfur- or carbon-centered stereogenicity. Recent advances in transition-metal catalysis, organocatalysis, and emerging electrocatalytic strategies have enabled efficient access to diverse chiral organosulfur frameworks, including sulfides, sulfoxides, sulfilimines, sulfoximines, and sulfinamides, with high levels of enantioselectivity. These methodologies have significantly expanded the synthetic toolbox for constructing C-S bonds under mild and sustainable conditions. This review provides a concise and critical overview of catalytic enantioselective C-S bond formation, emphasizing reaction design, catalytic systems, and mechanistic aspects of enantiocontrol. Key transformations such as asymmetric allylic substitution, conjugate addition, cross-coupling, photoredox-enabled processes, and emerging electrochemical approaches are discussed. Particular attention is given to strategies for the generation and control of sulfur-centered stereogenicity. Finally, current limitations and future opportunities, including dual catalysis, late-stage functionalization, and sustainable catalytic systems, are highlighted to guide further developments in asymmetric organosulfur chemistry.