Nickel‐Catalyzed Thermal Redox Functionalization of C(sp3)−H Bonds with Carbon Electrophiles. (31st March 2022)

• Record Type: Journal Article
• Authors: Gong, Yuxin; Su, Lei; Zhu, Zhaodong; Ye, Yang; Gong, Hegui
• Is Part Of: Angewandte Chemie. Volume 134:Number 22(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-03-31
• Subjects: C(sp3)–H Bonds -- Electrophiles -- Nickel -- Redox Reactions -- Thermal Reactions; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202201662
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: 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 t BuOO t Bu (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 Ni II salt. Abstract : Under thermal conditions, nickel‐catalyzed C(sp 3 )−H redox functionalization with carbon electrophiles has been advanced to forge value‐added C(sp 3 )−C bonds in good to excellent efficiency. This method emphasizes the use of external Zn as reductant and di‐ tert ‐butyl peroxide as an oxidant and shows remarkable compatibility with Ni‐catalysis.