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

Comprehensive Summary Although significant advances have been accomplished in the synthesis of α‐chiral carboxylic acid derivatives through Wolff rearrangement of α‐diazo ketones via different asymmetric catalytic mode including transition metal/photocatalysis, chiral Lewis base/photocatalysis, chiral SPA/photocatalysis and chiral NHC/photocatalysis, to the best of our knowledge, the construction of chiral carbon‐heteroatom bond through Wolff rearrangement remains underdeveloped. In this paper, 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, a broad substrate scope, scalable synthesis and versatile product functionalization, highlighting its practical value in constructing various chiral sulfur‐containing compounds. Additionally, this study significantly expand the utility of diazo compounds in Wolff rearrangement for asymmetric synthesis of sulfur‐containing compounds and carbene transfer reactions.