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<p>Transformations of various 2-O-trifluoromethanesulfonate derivatives of α-<span>d</span>-glucopyranosides, triggered by their treatment with azide anion, were investigated upon the synthesis of oligosaccharides related to moieties of the capsular polysaccharide from <i>Haemophilus influenzae</i> of type e. Based on the previously discovered fact of pyranose ring contraction as the alternative to the bimolecular nucleophilic substitution involving the azide anion, theoretical evaluations were carried out for the possibility to promote this reaction by other charged and neutral nucleophiles and bases. Analysis of the free activation energies and structural parameters for the found transition states revealed that the very azide anion possesses the unique ability to catalyze the ring contraction.</p>

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Theoretical investigation of anion-promoted contraction of the pyranose ring

  • 期刊论文

  • 发表日期：

    2025年3月1日

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  • A. G. Gerbst,
  • A. A. Kamneva,
  • D. V. Yashunsky,
  • N. E. Nifantiev

摘要

Transformations of various 2-O-trifluoromethanesulfonate derivatives of α-d-glucopyranosides, triggered by their treatment with azide anion, were investigated upon the synthesis of oligosaccharides related to moieties of the capsular polysaccharide from Haemophilus influenzae of type e. Based on the previously discovered fact of pyranose ring contraction as the alternative to the bimolecular nucleophilic substitution involving the azide anion, theoretical evaluations were carried out for the possibility to promote this reaction by other charged and neutral nucleophiles and bases. Analysis of the free activation energies and structural parameters for the found transition states revealed that the very azide anion possesses the unique ability to catalyze the ring contraction.