Huan-Huan Zhao, Xu-Gang Zhang, Haowen Jiang, Yi Zhao, Xiu‐Qin Hu, Peng‐Fei Xu
In this study, we developed a visible light-mediated C(sp 3 )–H amination strategy enabled by ligand-to-metal charge transfer (LMCT) and iron catalysis. The inexpensive Fe(NO 3 ) 3 ·9H 2 O affords a photoactive iron complex upon coordination with N-heteroaryl substrates, and the complex undergoes LMCT-induced β-homolysis to produce a high-valent Fe(IV)═O species. The Fe(IV)═O species promotes alkyl radical formation, enabling efficient C(sp 3 )–N bond construction. The reaction operates under mild conditions with broad functional group tolerance and excellent scalability, providing a practical platform for C(sp 3 )–H amination.