Enantioselective and Regiodivergent Skeletal Transformations of 1,2,3-Thiadiazoles to Alkylidene Dihydrothiophenes

By leveraging the Rh-catalyzed asymmetric skeletal editing of 1,2,3-thiadiazoles, we successfully achieve the ligand-controlled enantioselective and regiodivergent synthesis of structurally diverse 2- and 3-alkylidene 2,3-dihydrothiophenes. Late-stage structural editing of complex natural and drug molecules is also enabled.