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

Abstract

C(sp 3 )À 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 )À H bonds with organohalides to forge C(sp 3 )À 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 CÀ 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.