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 language | English |
|---|---|
| Pages (from-to) | 123-127 |
| Number of pages | 5 |
| Journal | Chemical Physics Letters |
| Volume | 723 |
| DOIs | |
| Publication status | Published - 16 May 2019 |
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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 journal › Article
}
TY - JOUR
T1 - Deacetylation of per-acetatylated glycopyranosides
T2 - An overall pattern for acidic catalyzis
AU - Nasibullin, R. T.
AU - Valiev, R. R.
AU - Faiskanova, K. M.
AU - Stepanova, E. V.
AU - Cherepanov, V. N.
AU - Filimonov, V. D.
AU - Sundholm, D.
PY - 2019/5/16
Y1 - 2019/5/16
N2 - 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.
AB - 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.
KW - Acid-catalyzed deacetylation
KW - Activation energy calculation
KW - Aryl glycosides
KW - Transition state modelling
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U2 - 10.1016/j.cplett.2019.03.022
DO - 10.1016/j.cplett.2019.03.022
M3 - Article
VL - 723
SP - 123
EP - 127
JO - Chemical Physics Letters
JF - Chemical Physics Letters
SN - 0009-2614
ER -