Synergistic Pd/Ni Dual-Catalyzed Cross-Coupling of Azaaryl Acetates with gem-Difluorinated Cyclopropanes

We herein report the development of a novel Pd/Ni dual-catalyzed ring-opening functionalization of gem-difluorinated cyclopropanes (gem-F₂CPs) with azaaryl acetates. This bimetallic catalytic strategy streamlines the diversity-oriented synthesis (DOS) of α-quaternary 2-fluoroallylic azaaryl acetates with features of a broad scope and excellent functional group tolerance, which enables the efficient late-stage transformation of natural product-derived gem-F₂CPs. The resulting α-quaternary azaaryl acetates could serve as a valuable platform to prepare other different fluoroallylic azaaryl scaffolds.