Direct conversion of cheap methylarenes to benzylic amines, which are essential structural units of important drugs, is of great significance. However, the known methodologies suffer from the requirement of noble metal catalysts, heavy metal residues or strong oxidants. Herein, the first biocompatible iron-catalyzed benzylic C (sp3)–H amination of methylarenes with N-fluorobenzenesulfonimide is described. The reactions of methylarenes bearing electron-donating groups and electron-withdrawing groups ran smoothly under ligand and additional oxidant free conditions. Both toluene derivatives and 8-methylquinoline can be aminated by the same iron catalyst.
