Photoredox aerobic oxidation of unreactive amine derivatives through LMCT excitation of copper dichloride

This work demonstrates a versatile oxidation system, a combination of CuCl2 and visible light, which is applicable to both C-H oxidation and N-demethylation and works for diverse categories of inert amine derivatives, including secondary and tertiary amides, sulfonamides, carbamates, and alpha-ketoamides. In addition, this ligand-to-metal charge transfer process uses molecular oxygen as a terminal oxidant and has a low cost catalytic system, broad functional group compatibility, easy availability of starting materials, and extraordinarily mild conditions. A preliminary mechanistic investigation indicates that the facile formation of a chlorine radical and the subsequent radical cascade reaction are involved in this photoredox process.

Automated summary

This work presents a versatile oxidation system using a combination of CuCl2 and visible light, which can be applied to both C-H oxidation and N-demethylation of inert amine derivatives. It offers a low-cost catalytic system, broad functional group compatibility, easy access to starting materials, and mild reaction conditions.