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.
Wang et al. (Mon,) studied this question.