A visible-light-promoted radical reaction system for azidation and halogenation of tertiary aliphatic C–H bonds

A highly tunable radical-mediated reaction system for the functionalization of tertiary aliphatic C–H bonds was developed. Reactions of various substrates with the Zhdankin azidoiodane reagent 1, Ru(bpy)(3)Cl(2), and visible light irradiation at room temperature gave C–H azidated or halogenated products in an easily controllable fashion. These reactions are efficient, selective, and compatible with complex substrates. They provide a potentially valuable tool for selectively labeling tertiary C–H bonds of organic and biomolecules with tags of varied chemical and biophysical properties for comparative functional studies.