Ni-Catalyzed Suzuki−Miyaura Coupling of (Hetero)aryl Halides with Fluorinated Boronic Esters

High Resolution Image Download MS PowerPoint Slide Electron-deficient polyfluorinated boron reagents have found little echo in Ni-catalyzed Suzuki−Miyaura reactions due to their proclivity for competing deboronation under basic conditions and their inherent difficulty to enable transmetallation events. Herein, we describe a Ni-catalyzed blueprint that enables the coupling of a broad range of electron-deficient polyfluorinated boronic esters and (hetero)aryl halides, including challenging substrate combinations. The strategy does not take recourse to specialized ligands and makes use of phenols as additives, offering not only a particularly facile transmetallation via the intermediacy of tetracoordinated boronates but also the ability to suppress parasitic deboronation events.