Solvent-free and direct C(sp³)-H amination of adamantanes by grinding

A facile, direct and environmentally benign conversion of C(sp ³)-H bonds to C(sp³)-N bonds using substoichiometric amount of aprotic superelectrophiles polyhalomethane-AlX₃ 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 to excellent yields. The advantages of this amination are atom economy, solvent-free, chemoselectivity, short reaction time and high yields.