Rhodium-Catalyzed Ligand-Controlled Chemoselective and Regioselective Coupling of gem -Difluorocyclopropanes with Alcohols

Abstract A ligand-controlled rhodium-catalyzed divergent defluorinative coupling of gem-difluorocyclopropanes with alcohols is reported. Monodentate phosphine ligands afford 1-alkoxy-1-arylpropan-2-ones via bis-defluorination in up to 83% yield, while bidentate ligands give Z-monofluoroalkenes via monodefluorination in up to 91% yield. Mechanistic studies reveal that alcohol acts as both an O-nucleophile and a hydride source. This work broadens the scope of the rhodium-catalyzed reaction of gem-difluorocyclopropanes and provides a unique catalytic strategy for controllable defluorination.