Construction of Sulfur(IV)‐Chiral Six‐Membered Heterocycles by Pd‐Catalyzed Asymmetric (4+2) Dipolar Cyclization

Abstract Chiral sulfur‐containing compounds play an important role in asymmetric catalysis and synthesis, chiral pharmaceuticals, and chiral materials. While great progress has been made in the synthesis of these compounds, the asymmetric catalytic synthesis of chiral sulfur‐containing heterocycles remains relatively limited compared to acyclic ones. In this study, we successfully report an efficient and highly selective synthesis of structurally diverse chirality‐at‐sulfur(IV) six‐membered heterocycles under mild conditions via a Pd‐catalyzed asymmetric (4+2) dipolar cyclization. More importantly, these products enable the enantioselective preparation of a variety of other S‐stereogenic derivatives.