Palladium-catalyzed cyanation and alkynylation of allylic gem-difluorides via Hiyama-type coupling

Abstract

We report a palladium-catalyzed Hiyama-type defluorinative cross-coupling of allylic gem-difluorides with trimethylsilyl cyanide and silylalkynes via selective C–F bond activation. The reaction involves oxidative addition, Si–F-assisted transmetalation, and reductive elimination, enabling efficient construction of C(sp³)–CN and C(sp³)–C(sp) bonds under mild, additive-free conditions. It features broad substrate scope, excellent functional group tolerance, and high regio- and Z-selectivity, affording diverse monofluorinated alkenes in good to excellent yields. The resulting fluoroalkenes serve as versatile intermediates for downstream functionalization, highlighting the synthetic utility of this Si–F-driven platform.