title: Unactivated C(sp3)-H Bond Functionalization of Alkyl Nitriles with Vinylarenes and Mechanistic Studies.
abstract: The first example of a metal-free unactivated C(sp3)-H bond functionalization of alkyl nitriles with terminal vinylarenes to provide γ-ketonitrile derivatives is described. This protocol features simple operations, a broad substrate scope, and atom and step economy. In addition, Cu-catalyzed C(sp3)-H bond functionalization of azodiisobutyronitrile (AIBN) and analogues with terminal vinylarenes to generate γ-ketonitriles was also studied. A preliminary free-radical pathway was confirmed by capturing an alkyl radical, and a conjugate system was found that can stabilize radical intermediates and be in favor of this transformation. Density functional theory (DFT) calculations also provide important evidence of the free-radical pathway.
authors.affiliation: Technical Institute of Physics and Chemistry & University of Chinese Academy of Sciences, Chinese Academy of Sciences , Beijing, 100190, China.
authors.forename: Xing-Wang
authors.initials: XW
authors.lastname: Lan
authors.affiliation: Technical Institute of Physics and Chemistry & University of Chinese Academy of Sciences, Chinese Academy of Sciences , Beijing, 100190, China.
authors.forename: Nai-Xing
authors.initials: NX
authors.lastname: Wang
authors.affiliation: Technical Institute of Physics and Chemistry & University of Chinese Academy of Sciences, Chinese Academy of Sciences , Beijing, 100190, China.
authors.forename: Cui-Bing
authors.initials: CB
authors.lastname: Bai
authors.affiliation: School of Chemistry, Beijing Institute of Technology , Beijing 100081, China.
authors.forename: Cui-Lan
authors.initials: CL
authors.lastname: Lan
authors.affiliation: Technical Institute of Physics and Chemistry & University of Chinese Academy of Sciences, Chinese Academy of Sciences , Beijing, 100190, China.
authors.forename: Tong
authors.initials: T
authors.lastname: Zhang
authors.affiliation: School of Chemistry, Beijing Institute of Technology , Beijing 100081, China.
authors.forename: Shi-Lu
authors.initials: SL
authors.lastname: Chen
authors.affiliation: Department of Chemistry, William Paterson University of New Jersey , 300 Pompton Road, Wayne, New Jersey 07470, United States.
authors.forename: Yalan
authors.initials: Y
authors.lastname: Xing