Transition-Metal-Catalyzed Amination of Aryl Fluorides

摘要

Arene activation via transition-metal (TM) eta(6)-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 eta(6)-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 eta(6)-arene complex, and the hemilabile ligand significant promoted the arene dissociation.