Theoretical Calculations for the 1,4-Hydrogen Shift of 1-Hydroxyallyl Radicals Leading to α-Keto Radicals; Prediction of Facilitation by 1-Amino and 3-Tin Substituents

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Author(s)

    • Matsubara Hiroshi
    • Department of Chemistry, Graduate School of Science, Osaka Prefecture University
    • Kawamoto Takuji
    • Department of Chemistry, Graduate School of Science, Osaka Prefecture University
    • Fukuyama Takahide
    • Department of Chemistry, Graduate School of Science, Osaka Prefecture University
    • Ryu Ilhyong
    • Department of Chemistry, Graduate School of Science, Osaka Prefecture University|Department of Applied Chemistry, National Chiao Tung University

Abstract

<p>DFT calculations were carried out to elucidate the 1,4-hydrogen shift of 1-hydroxyallyl radicals to give α-keto radicals. The 1,4-H shift is predicted to be exothermic with large energy barriers. However, the energy barriers of 1,4-H shift were predicted to be lowered significantly by 1-amino and 3-tin substituents. The results agreed well with the experimental results shown by the stannylcarbonylation of alkynes in the presence of an amine, in which the 1,4-H shift of substituted 1-hydroxyallyl radicals has been proposed as a key step.</p>

Journal

  • Chemistry Letters

    Chemistry Letters 47(9), 1197-1199, 2018

    The Chemical Society of Japan

Codes

  • NII Article ID (NAID)
    130007472130
  • Text Lang
    ENG
  • ISSN
    0366-7022
  • Data Source
    J-STAGE 
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