Enantioselective Thia‐Wolff Rearrangement via Cooperative Catalysis of Rhodium/Chiral Brønsted Acid: A Facile Access to Enantioenriched α‐Sulfenylated Amides †

Comprehensive Summary The first catalytic asymmetric thia‐Wolff rearrangement between α‐aryl α‐diazothioesters and amines has been successfully achieved under cooperative rhodium/chiral phosphoric acid catalysis, which provides efficient access to synthetically valuable chiral α‐sulfenylated amide architectures. This protocol features mild reaction conditions, high efficiency, excellent stereoselectivity, and a broad substrate scope.