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

Hiroshi Matsubara*, Takuji Kawamoto, Takahide Fukuyama, Ilhyong Ryu

*Corresponding author for this work

    Research output: Contribution to journalArticlepeer-review

    3 Scopus citations

    Abstract

    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.

    Original languageEnglish
    Pages (from-to)1197-1199
    Number of pages3
    JournalChemistry Letters
    Volume47
    Issue number9
    DOIs
    StatePublished - Jan 2018

    Keywords

    • 1,4-Hydrogen transfer
    • 1-Hydroxyallyl radical
    • DFT calculation

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