Palladium-Catalyzed Defluorinative Cyanation of gem-Difluorinated Cyclopropanes for the Synthesis of 2-Fluoroallylic Nitriles.

We report a palladium-catalyzed ring-opening defluorinative cyanation of gem-difluorinated cyclopropanes (gem-DFCPs) with Zn(CN)2 as the cyanide source. The reaction proceeds smoothly via a sequence of regioselective C-C activation, C-F cleavage, and C-CN formation, providing precise access to synthetically appealing 2-fluoroallylic nitriles with features of a broad substrate scope, extraordinary functional group compatibility, and excellent Z-selectivity. The late-stage modification of gem-DFCPs derived from bioactive complex molecules and medicinally relevant scaffolds enhanced the practicality of this reaction.