Site-Selective Magnesiation of Multifluorinated Arenes Catalyzed by Rhodium–Aluminum Bimetallic Complexes

We report the site-selective C–F magnesiation of multifluorinated arenes catalyzed by Rh–Al bimetallic complexes to prepare synthetically important fluorine-containing organomagnesium reagents. We clarified that the catalyst-control site-selectivity stems from the steric and electronic environments of the substrates. The protocol can be applied to the efficient synthesis of fluorine-containing pharmaceuticals and liquid crystal molecules.