Palladium-Catalyzed Cyanation and Alkynylation of Allylic gem-Difluorides via Hiyama-Type Coupling

Abstract

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