Enantioselective Synthesis of α-Chiral Sulfonates through Palladium-Catalyzed Tsuji-Trost Sulfonylation with Sulfur Dioxide

α-Chiral sulfonates have remained largely uncharted territory, primarily due to the intrinsic difficulties associated with achieving stereocontrol. In this study, we present an innovative three-component palladium-catalyzed asymmetric Tsuji-Trost sulfonylation protocol, which introduces a novel strategy for the synthesis of enantiomerically enriched α-chiral sulfonates, utilizing S(VI) complexes as intermediates. This method is versatile, applicable to a diverse array of allylic acetates and alcohols, thereby allowing for the efficient synthesis of α-chiral sulfonates with high yields, exceptional regio- and enantioselectivities (up to 99% ee). In conclusion, this strategy offers a practical and efficient route for the generation of chiral α-substituted linear allylic sulfonates.