SCF ₃ -Alkenes Unlocked: A Gateway via Cu(I)-Catalyzed Stereocontrolled Cross-Coupling

The SCF 3 group has emerged as a key motif in medicinal and agrochemical chemistry. While synthetic methods to access aryl, alkynyl, and alkyl SCF 3 -derivatives are well-established, access to stereocontrolled SCF 3 -disubstituted alkenes remains challenging, with existing methods falling short on selectivity and substrate scope. Here we report a versatile Cu(I)-catalyzed cross-coupling that unlocks modular, stereodefined access to ( E )-, ( Z )-, and ( 1,1′ )-disubstituted SCF 3 -alkenes under mild, user-friendly conditions - breaking through key limitations of previous approaches. This scalable protocol exhibits broad functional group tolerance and handles complex, pharma- and agro-relevant substrates with ease. Moreover, the SCF 3 -alkenes serve as versatile platforms for selective postfunctionalization. Mechanistic evidence points to a two-electron pathway involving a hypervalent silicon intermediate, shedding light on this novel transformation.