Abstract A facile, direct and environmentally benign conversion of C (sp 3)–H bonds to C (sp 3)–N bonds using substoichiometric amount of aprotic superelectrophiles polyhalomethane– AlX 3 has been achieved by grinding under solvent-free conditions at room temperature in air. It is a general and simple method for the direct amination of adamantanes, and a series of aminoadamantanes of azoles, arylamines or heteroarylamines were obtained in good ...