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  • 标题:Visible-Light-Induced Alkoxyl Radicals Enable α-C(sp 3)-H Bond Allylation
  • 本地全文:下载
  • 作者:Jing Zhang ; Dan Liu ; Song Liu
  • 期刊名称:iScience
  • 印刷版ISSN:2589-0042
  • 出版年度:2020
  • 卷号:23
  • 期号:1
  • 页码:1-129
  • DOI:10.1016/j.isci.2019.100755
  • 语种:English
  • 出版社:Elsevier
  • 摘要:SummaryThe alkoxyl radical is an essential reactive intermediate in mechanistic studies and organic synthesis with hydrogen atom transfer (HAT) reactivity. However, compared with intramolecular 1,5-HAT or intermolecular HAT of alkoxyl radicals, the intramolecular 1,2-HAT reactivity has been limited to theoretical studies and rarely synthetically utilized. Here we report the first selective 1,2-HAT of alkoxyl radicals for α-C(sp3)-H bond allylation of α-carbonyl, α-cyano, α-trifluoromethyl, and benzylic N-alkoxylphthalimides. The mechanistic probing experiments, electron paramagnetic resonance (EPR) studies, and density functional theory (DFT) calculations confirmed the 1,2-HAT reactivity of alkoxyl radicals, and the use of protic solvents lowered the activation energy by up to 10.4 kcal/mol to facilitate the α-C(sp3)-H allylation reaction.Graphical AbstractDisplay OmittedHighlights•1,2-Hydrogen atom transfer (HAT) of alkoxyl radical enables α-C(sp3)-H allylation•α-Carbonyl, α-cyano, α-trifluoromethyl, and benzylic C(sp3)-H bonds are applicable•Mechanistic and electron paramagnetic resonance (EPR) studies confirmed 1,2-HAT•DFT calculations explained the methanol acceleration of alkoxyl radical 1,2-HATOrganic Chemistry; Organic Reaction; Physical Organic Chemistry
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