A General Platform for <i>S</i> ‐Stereogenic α‐Fluoroalkyl S(IV/VI) Compounds via Enantioselective Radical Fluoroalkylation of Sulfenamides

ABSTRACT α‐Fluoroalkyl‐substituted high‐valent sulfur motifs are important structural elements in fluorinated molecule design and exhibit broad application potential in diverse fields. However, access to S ‐stereogenic α‐fluoroalkyl S(IV/VI) compounds still relies largely on classical resolution, resulting in limited efficiency and selectivity. We herein report a copper‐catalyzed asymmetric radical C–S cross‐coupling that effectively tames highly reactive α‐fluoroalkyl radicals, enabled by a sequential stereodiscrimination–chirality transfer strategy, providing rapid access to S ‐chiral α‐fluoroalkyl sulfilimines. Integrated with downstream transformations, this reaction serves as a general and systematic platform for S ‐chiral α‐fluoroalkyl S(IV/VI) compounds. The synthetic utility of the method is demonstrated by gram‐scale synthesis and concise access to diverse chiral fluoroalkyl reagents and bioisosteres of sulfur‐containing drugs.