Xinhua Wang, Yuyuan Mao, Shengqing Ye, Xiaoyu Zhou, Jie Wu, Shaoyu Li
The asymmetric hydrosulfonylation of α,β-unsaturated carbonyls represents a significant goal in accessing α-chiral sulfones due to its high atom and step efficiency. In contrast to the well-established radical sulfonylation, the classical Michael addition using sulfonyl anions as nucleophiles for assembling α-chiral sulfone structures remains elusive and challenging. In this work, we introduce an organocatalytic enantioselective Michael addition of α,β-unsaturated carbonyls with sulfur dioxide insertion-enabled γ-keto sulfinates as the nucleophiles, which provides an alternative pathway for producing highly enantioenriched α-chiral sulfone derivatives with high atom economy. Mechanistic details of the transformation pathway and stereochemical induction were systematically verified through controlled experiments and DFT calculations.