Magnesiation of Phenol Derivatives Catalyzed by a Rhodium–Aluminum Complex

Here we describe the generation of aryl Grignard reagents from phenol derivatives via C–O bond activation cooperatively catalyzed by Rh–Al heterobimetallic complexes. We discovered that the electron-rich arylmagnesium reagents could be efficiently prepared from the corresponding aryl carbamates, whereas the π-extended arylmagnesium reagents were obtained from the corresponding aryl ethers. This methodology enables the efficient conversion of a broad range of phenol derivatives into the corresponding Grignard reagents, which can subsequently react with various electrophiles to yield a diverse array of organic compounds.