A new look at acid catalyzed deacetylation of carbohydrates: A regioselective synthesis and reactivity of 2-O-acetyl aryl glycopyranosides

Elena V. Stepanova, Marina O. Nagornaya, Victor D. Filimonov, Rashid R. Valiev, Maxim L. Belyanin, Anna K. Drozdova, Victor N. Cherepanov

Результат исследований: Материалы для журналаСтатья

2 Цитирования (Scopus)

Выдержка

In the present work we report that acetyl groups of per – acetylated aryl glycosides have different reactivity during the acidic deacetylation using HCl/EtOH in CHCl3, which leads to preferential deacetylation at O-3, O-4 and O-6. Thereby, the one-step preparation of 2-O-acetyl aryl glycosides with simple aglycon was accomplished for the first time. It was proved that the found reagent is to be general and unique for the preparation of series of 2-О-acetyl aryl glycosides. We have determined the influence of both carbohydrate moiety and the aglycon on the selectivity of deacetylation reaction by kinetic experiments. Using DFT/B3LYP/6-31G(d,p) and semi-empirical АМ1 methods we have found that the highest activation barrier is for 2-О-acetyl group. This completely explains the least reactivity of 2-О-acetyl group.

Язык оригиналаАнглийский
Страницы (с-по)60-66
Число страниц7
ЖурналCarbohydrate Research
Том458-459
DOI
СостояниеОпубликовано - 22 мар 2018

Отпечаток

Glycosides
Carbohydrates
Acids
Discrete Fourier transforms
Chemical activation
Kinetics
Experiments

ASJC Scopus subject areas

  • Analytical Chemistry
  • Biochemistry
  • Organic Chemistry

Цитировать

A new look at acid catalyzed deacetylation of carbohydrates : A regioselective synthesis and reactivity of 2-O-acetyl aryl glycopyranosides. / Stepanova, Elena V.; Nagornaya, Marina O.; Filimonov, Victor D.; Valiev, Rashid R.; Belyanin, Maxim L.; Drozdova, Anna K.; Cherepanov, Victor N.

В: Carbohydrate Research, Том 458-459, 22.03.2018, стр. 60-66.

Результат исследований: Материалы для журналаСтатья

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abstract = "In the present work we report that acetyl groups of per – acetylated aryl glycosides have different reactivity during the acidic deacetylation using HCl/EtOH in CHCl3, which leads to preferential deacetylation at O-3, O-4 and O-6. Thereby, the one-step preparation of 2-O-acetyl aryl glycosides with simple aglycon was accomplished for the first time. It was proved that the found reagent is to be general and unique for the preparation of series of 2-О-acetyl aryl glycosides. We have determined the influence of both carbohydrate moiety and the aglycon on the selectivity of deacetylation reaction by kinetic experiments. Using DFT/B3LYP/6-31G(d,p) and semi-empirical АМ1 methods we have found that the highest activation barrier is for 2-О-acetyl group. This completely explains the least reactivity of 2-О-acetyl group.",
keywords = "Aryl glycosides, Partially acylated carbohydrates, Reactivity, Regioselective deacetylation, Transition states modeling",
author = "Stepanova, {Elena V.} and Nagornaya, {Marina O.} and Filimonov, {Victor D.} and Valiev, {Rashid R.} and Belyanin, {Maxim L.} and Drozdova, {Anna K.} and Cherepanov, {Victor N.}",
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T1 - A new look at acid catalyzed deacetylation of carbohydrates

T2 - A regioselective synthesis and reactivity of 2-O-acetyl aryl glycopyranosides

AU - Stepanova, Elena V.

AU - Nagornaya, Marina O.

AU - Filimonov, Victor D.

AU - Valiev, Rashid R.

AU - Belyanin, Maxim L.

AU - Drozdova, Anna K.

AU - Cherepanov, Victor N.

PY - 2018/3/22

Y1 - 2018/3/22

N2 - In the present work we report that acetyl groups of per – acetylated aryl glycosides have different reactivity during the acidic deacetylation using HCl/EtOH in CHCl3, which leads to preferential deacetylation at O-3, O-4 and O-6. Thereby, the one-step preparation of 2-O-acetyl aryl glycosides with simple aglycon was accomplished for the first time. It was proved that the found reagent is to be general and unique for the preparation of series of 2-О-acetyl aryl glycosides. We have determined the influence of both carbohydrate moiety and the aglycon on the selectivity of deacetylation reaction by kinetic experiments. Using DFT/B3LYP/6-31G(d,p) and semi-empirical АМ1 methods we have found that the highest activation barrier is for 2-О-acetyl group. This completely explains the least reactivity of 2-О-acetyl group.

AB - In the present work we report that acetyl groups of per – acetylated aryl glycosides have different reactivity during the acidic deacetylation using HCl/EtOH in CHCl3, which leads to preferential deacetylation at O-3, O-4 and O-6. Thereby, the one-step preparation of 2-O-acetyl aryl glycosides with simple aglycon was accomplished for the first time. It was proved that the found reagent is to be general and unique for the preparation of series of 2-О-acetyl aryl glycosides. We have determined the influence of both carbohydrate moiety and the aglycon on the selectivity of deacetylation reaction by kinetic experiments. Using DFT/B3LYP/6-31G(d,p) and semi-empirical АМ1 methods we have found that the highest activation barrier is for 2-О-acetyl group. This completely explains the least reactivity of 2-О-acetyl group.

KW - Aryl glycosides

KW - Partially acylated carbohydrates

KW - Reactivity

KW - Regioselective deacetylation

KW - Transition states modeling

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