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

    Research output: Contribution to journal › Article

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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.

    LanguageEnglish
    Pages60-66
    Number of pages7
    JournalCarbohydrate Research
    Volume458-459
    DOIs
    Publication statusPublished - 22 Mar 2018

    Fingerprint

    Glycosides
    Carbohydrates
    Acids
    Discrete Fourier transforms
    Chemical activation
    Kinetics
    Experiments

    Keywords

    • Aryl glycosides
    • Partially acylated carbohydrates
    • Reactivity
    • Regioselective deacetylation
    • Transition states modeling

    ASJC Scopus subject areas

    • Analytical Chemistry
    • Biochemistry
    • Organic Chemistry

    Cite this

    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.

    In: Carbohydrate Research, Vol. 458-459, 22.03.2018, p. 60-66.

    Research output: Contribution to journal › Article

    Stepanova, EV, Nagornaya, MO, Filimonov, VD, Valiev, RR, Belyanin, ML, Drozdova, AK & Cherepanov, VN 2018, 'A new look at acid catalyzed deacetylation of carbohydrates: A regioselective synthesis and reactivity of 2-O-acetyl aryl glycopyranosides' Carbohydrate Research, vol. 458-459, pp. 60-66. https://doi.org/10.1016/j.carres.2018.02.003
    Stepanova EV, Nagornaya MO, Filimonov VD, Valiev RR, Belyanin ML, Drozdova AK et al. A new look at acid catalyzed deacetylation of carbohydrates: A regioselective synthesis and reactivity of 2-O-acetyl aryl glycopyranosides. Carbohydrate Research. 2018 Mar 22;458-459:60-66. https://doi.org/10.1016/j.carres.2018.02.003
    Stepanova, Elena V. ; Nagornaya, Marina O. ; Filimonov, Victor D. ; Valiev, Rashid R. ; Belyanin, Maxim L. ; Drozdova, Anna K. ; Cherepanov, Victor N. / A new look at acid catalyzed deacetylation of carbohydrates : A regioselective synthesis and reactivity of 2-O-acetyl aryl glycopyranosides. In: Carbohydrate Research. 2018 ; Vol. 458-459. pp. 60-66.
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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.",
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    AU - Filimonov, Victor D.

    AU - Valiev, Rashid R.

    AU - Belyanin, Maxim L.

    AU - Drozdova, Anna K.

    AU - Cherepanov, Victor N.

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    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.

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    KW - Regioselective deacetylation

    KW - Transition states modeling

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