Reactions that directly install nitrogen into C—H bonds of complex molecules are significant due to their ability to immediately change the chemical and biological properties of a given molecule. While selective intramolecular C—H amination reactions are known, intermolecular C—H amination reactions with high reactivity and selectivity are scarce. Achieving high levels of reactivity while maintaining excellent site-selectivity and functional group tolerance remains an important challenge for intermolecular C—H amination. We report a novel manganese perchlorophthalocyanine catalyst [Mn(ClPc)] for a highly site-selective intermolecular benzylic C—H amination of bioactive molecules and natural products. [Mn(ClPc)] is selective for benzylic C—H bonds over other C—H bond types and selects among multiple benzylic C—H bonds based on their electronic and steric properties.