Deacetylation of per-acetatylated glycopyranosides

An overall pattern for acidic catalyzis

R. T. Nasibullin, R. R. Valiev, K. M. Faiskanova, E. V. Stepanova, V. N. Cherepanov, V. D. Filimonov, D. Sundholm

Research output: Contribution to journalArticle

Abstract

Acetyl protecting groups are commonly used in carbohydrate chemistry. Partially acetylated arylglycosides are not only useful building blocks in syntheses, but they are also substantial for plant metabolism. Nonselective base catalysis is often used for removing the acetyl groups. Even though acid-catalyzed deacetylation might be more selective, it is seldom used in carbohydrate chemistry, because it has not been thoroughly investigated. In this work, we study the acid-catalyzed deacetylation of per-acetylated phenyl glycosides experimentally and computationally by using density functional theory (DFT) calculations. Based on quantum modeling, we design a general scheme for the stepwise acid-catalyzed deacetylation of arylglycosides per-acetates. The approach can also be applied on gluco- and galactopyranosides. We have studied the deacetylation reaction in solvents of different polarity and found that the activation barriers of the stepwise deacetylation mechanism increase with increasing polarity of the solvent.

Original languageEnglish
Pages (from-to)123-127
Number of pages5
JournalChemical Physics Letters
Volume723
DOIs
Publication statusPublished - 16 May 2019

Fingerprint

carbohydrates
acids
Acids
polarity
Carbohydrates
chemistry
glucosides
metabolism
Glycosides
Galactose
Metabolism
Catalysis
catalysis
Density functional theory
acetates
Acetates
Chemical activation
activation
density functional theory
synthesis

Keywords

  • Acid-catalyzed deacetylation
  • Activation energy calculation
  • Aryl glycosides
  • Transition state modelling

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Deacetylation of per-acetatylated glycopyranosides : An overall pattern for acidic catalyzis. / Nasibullin, R. T.; Valiev, R. R.; Faiskanova, K. M.; Stepanova, E. V.; Cherepanov, V. N.; Filimonov, V. D.; Sundholm, D.

In: Chemical Physics Letters, Vol. 723, 16.05.2019, p. 123-127.

Research output: Contribution to journalArticle

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AU - Filimonov, V. D.

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