Palladium-Catalyzed Dearomative Fluoroallylation of Pyrroles with gem-Difluorinated Cyclopropanes

We herein report the development of a novel Pd-catalyzed dearomative functionalization of pyrroles with gem-difluorinated cyclopropanes (gem-F₂CPs). This dearomative/ring-opening strategy streamlines the diversity-oriented synthesis (DOS) of α-quaternary 2-fluoroallylic 2H-pyrroles with a broad scope and excellent functional group tolerance, which enables the efficient late-stage transformation of complex bioactive molecule-derived gem-F₂CPs. Derivation of the resulting fluoroallylic 2H-pyrroles to different synthetically useful fluoroallylic 2H-pyrrole motifs demonstrated the synthetic value of this methodology.