Nickel‐Catalyzed Thermal Redox Functionalization of C(sp3)−H Bonds with Carbon Electrophiles**

Abstract

AbstractC(sp3)−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(sp3)−H bonds with organohalides to forge C(sp3)−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‐α‐ 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 NiII salt.