Synergistic\nPd/Ni Dual-Catalyzed Cross-Coupling of\nAzaaryl Acetates with <i>gem</i>-Difluorinated Cyclopropanes

We\nherein report the development of a novel Pd/Ni dual-catalyzed\nring-opening functionalization of <i>gem</i>-difluorinated\ncyclopropanes (<i>gem</i>-F<sub>2</sub>CPs) with azaaryl\nacetates. This bimetallic catalytic strategy streamlines the diversity-oriented\nsynthesis (DOS) of α-quaternary 2-fluoroallylic azaaryl acetates\nwith features of a broad scope and excellent functional group tolerance,\nwhich enables the efficient late-stage transformation of natural product-derived <i>gem</i>-F<sub>2</sub>CPs. The resulting α-quaternary azaaryl\nacetates could serve as a valuable platform to prepare other different\nfluoroallylic azaaryl scaffolds.