Copper-mediated direct ortho-C-H amination of arenes has been accomplished with the aid of easily removable bidentate pyridine N-oxide as a directing group. The use of free cyclic secondary amines and anilines as aminating agents and inexpensive copper acetate makes the strategy more effective and favorable from the economic point of view. This reaction is compatible with a wide range of functional groups to synthesize a variety of amine-containing products of high interest. This method also allows the short synthesis of the central scaffold of pharmaceutically relevant Staphylococcus aureus Sortase A inhibitors.