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 , Ru(bpy)Cl, 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.