Copper Catalyzed C(sp3)- H Bond Alkylation via Photoinduced Ligand-to-Metal Charge Transfer

Utilizing catalytic CuCl2 we report the functionalization of numerous feedstock chemicals via the coupling of unactivated C(sp(3))-H bonds with electron-deficient olefins. The active cuprate catalyst undergoes Ligand-to-Metal Charge Transfer (LMCT) to enable the generation of a chlorine radical which acts as a powerful hydrogen atom transfer reagent capable of abstracting strong electron-rich C(sp(3))-H bonds. Of note is that the chlorocuprate catalyst is an exceedingly mild oxidant (0.5 V vs SCE) and that a proposed protodemetalation mechanism offers a broad scope of electron-deficient olefins, offering high diastereoselectivity in the case of endocyclic alkenes. The coupling of chlorine radical generation with Cu reduction through LMCT enables the generation of a highly active HAT reagent in an operationally simple and atom economical protocol.

Automated summary

By utilizing catalytic CuCl2, various feedstock chemicals can be functionalized through the coupling of unactivated C(sp(3))-H bonds with electron-deficient olefins. This reaction, enabled by Ligand-to-Metal Charge Transfer (LMCT), generates a chlorine radical capable of abstracting strong electron-rich C(sp(3))-H bonds. The protocol offers a simple operation and atom economical approach to generate a highly active hydrogen atom transfer reagent.