Phosphorus Coordination Chemistry in Catalysis: Air Stable P(III)-Dications as Lewis Acid Catalysts for the Allylation of C–F Bonds

Abstract

Modification of C–F bonds with main-group catalysts has typically employed electron-deficient Lewis superacids in high oxidation states, and the challenges of preparing and handling such species have prevented broader adoption of metal-free reduction protocols. Here, we show that a hemilabile ligand coordinated to an easily accessed P(III) center imparts air stability without sacrificing the ability to activate C–F bonds. Catalytic C–C coupling of benzyl fluorides with allylsilanes was achieved using a P(III) complex under benchtop conditions. This application of coordination chemistry principles to main-group Lewis acids reveals a new strategy for controlling catalysis.