Ru(II)-Catalyzed Amination of Aryl Fluorides via η6-Coordination.

We developed a Ru/hemilabile-ligand-catalyzed nucleophilic aromatic substitution (SNAr) of aryl fluorides as the limiting reagents. Significant ligand enhancement was demonstrated by the engagement of both electron-rich and neutral arenes in the SNAr amination without using excess arenes. Preliminary mechanistic studies revealed that the nucleophilic substitution proceeds on a η6-complex of the Ru catalyst and the substrate, and the hemilabile ligand facilitates dissociation of products from the metal center.