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

The SCF₃ group has emerged as a key motif in medicinal and agrochemical chemistry. While synthetic methods to access aryl, alkynyl, and alkyl SCF₃-derivatives are well-established, access to stereocontrolled SCF₃-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 (<i>E</i>)-, (<i>Z</i>)-, and (<i>1,1'</i>)-disubstituted SCF₃-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 SCF₃-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.