Transition-Metal-Catalyzed Amination of Aryl Fluorides

Abstract

Arene activation via transition-metal (TM) η6-coordination has merged as a powerful method to diversify the aromatic C–F bond, which is relatively less reactive due to its high bond energy. However, this strategy in general requires to use largely excess arenes or TM η6-complexes as the substrates. Herein, we highlight our recent work on the catalytic SNAr amination of electron-rich and electron-neutral aryl fluorides that are inert in classical SNAr reactions. This protocol enabled by a Ru/hemilabile ligand catalyst covers a broad scope of substrates without wasting arenes. Mechanistic studies revealed that the nucleo­philic substitution proceeded on a Ru η6-arene complex, and the hemilabile ligand significant promoted the arene dissociation.