Advancing Sulfinyl Radical Chemistry: An Asymmetric Smiles Rearrangement with Chiral Sulfoxides

Abstract Chiral N‐sulfinyl amides have recently emerged as powerful reagents for asymmetric, radical‐mediated Smiles rearrangements, imparting excellent levels of relative and absolute stereocontrol in the intra‐ and intermolecular translocation of aryl groups. Here, we capitalize on the much more readily available and abundant chiral sulfoxides, which, in combination with radical precursors and alkylating reagents, afford enantioenriched sulfur‐containing molecules via a photocatalytic multicomponent asymmetric sulfinyl‐Smiles rearrangement with retention of “SO”. This cascade process involves radical addition, a stereocontrolled 1,5‐aryl migration, and subsequent C─S bond formation, forging two new C─C bonds and a C─S bond in a single step under mild conditions. The resulting enantioenriched sulfur‐containing scaffolds are not only common in pharmaceuticals and bioactive compounds but also serve as versatile synthetic intermediates, as demonstrated by their efficient derivatization into diverse motifs.