The direct amination of aliphatic C−H bonds has remained one of the most tantalizing transformations in organic chemistry. Herein, we report on a unique catalyst system, which enables the elusive intermolecular C(sp³)−H amination. This practical synthetic strategy provides access to aminated building blocks and fosters innovative multiple C−H amination within a new approach to aminated heterocycles. The synthetic utility is demonstrated by the synthesis of four relevant pharmaceuticals.