Nickel-Catalyzed Thermal Redox Functionalization of C(sp3)-H Bonds with Carbon Electrophiles

C(sp(3))-H bond coupling with carbon electrophiles remains rarely explored under thermo-driven hydrogen atom transfer (HAT) conditions due to the challenge of integrating oxidation and reduction in a single operation. We report here a Ni-catalyzed arylation and alkylation of C(sp(3))-H bonds with organohalides to forge C(sp(3))-C bonds by merging economical Zn and tBuOOtBu (DTBP) as the external reductant and oxidant. The mild and easy-to-operate protocol enables facile carbofunctionalization of N-/O-alpha- and cyclohexane C-H bonds, and preparation of a few intermediates of bioactive compounds and drug derivatives. Preliminary mechanistic studies implied addition of an alkyl radical to a Ni-II salt.

Automated summary

In this study, a mild and easy-to-operate Ni-catalyzed arylation and alkylation reaction was reported using Zn and tBuOOtBu as the external reductant and oxidant. This reaction enables carbofunctionalization of C(sp(3))-H bonds and preparation of intermediates of bioactive compounds and drug derivatives.