Regioselective Difunctionalization of <i>gem</i> -Difluorocyclopropanes via Palladium-Catalyzed Defluorinative Coupling

<i>gem</i>-Difluorocyclopropanes (<i>gem</i>-DFCPs) serve as versatile building blocks in synthetic chemistry, generally enabling the preparation of functional molecules through ring-opening substitution. Here, we disclose an efficient palladium-catalyzed difunctionalization of <i>gem</i>-DFCPs using alcohols or phenols as nucleophiles to construct alkoxy- or aryloxy-functionalized allyl ethers. This reaction is operationally simple, displays broad functional group tolerance, and exhibits excellent chemo- and regioselectivity. Investigations into the mechanism suggest that the secondary C-F substitution proceeds via a monofluorinated four-membered palladacycle intermediate.