On the Origin of Regioselectivity in Palladium-Catalyzed Oxidation of Glucosides
| Autor: | Jeroen D. C. Codée, F. Matthias Bickelhaupt, Christopher A. Vis, Trevor A. Hamlin, Ieng Chim (Steven) Wan, Niek N. H. M. Eisink, Casper de Boer, Adriaan J. Minnaard, Martin D. Witte, Nittert Marinus |
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| Přispěvatelé: | Chemical Biology 2, Theoretical Chemistry, AIMMS, Chemistry and Pharmaceutical Sciences |
| Jazyk: | angličtina |
| Rok vydání: | 2021 |
| Předmět: |
Organic Chemistry
Carbohydrates chemistry.chemical_element Regioselectivity Ring (chemistry) Photochemistry Oxygen Gibbs free energy Catalysis symbols.namesake Density functional calculations Energy decomposition analysis chemistry Oxidation symbols Density functional theory SDG 7 - Affordable and Clean Energy Physical and Theoretical Chemistry Theoretical Chemistry Carbon Palladium |
| Zdroj: | European Journal of Organic Chemistry, 2021(4), 632-636. WILEY-V C H VERLAG GMBH Wan, I C, Hamlin, T A, Eisink, N N H M, Marinus, N, de Boer, C, Vis, C A, Codée, J D C, Witte, M D, Minnaard, A J & Bickelhaupt, F M 2021, ' On the Origin of Regioselectivity in Palladium-Catalyzed Oxidation of Glucosides ', European Journal of Organic Chemistry, vol. 2021, no. 4, pp. 632-636 . https://doi.org/10.1002/ejoc.202001453 European Journal of Organic Chemistry, 2021, 4, pp. 632-636 European Journal of Organic Chemistry, 2021, 632-636 European Journal of Organic Chemistry European Journal of Organic Chemistry, 2021(4), 632-636. Wiley-VCH Verlag |
| ISSN: | 1434-193X |
| DOI: | 10.1002/ejoc.202001453 |
| Popis: | The palladium-catalyzed oxidation of glucopyranosides has been investigated using relativistic density functional theory (DFT) at ZORA-BLYP-D3(BJ)/TZ2P. The complete Gibbs free energy profiles for the oxidation of secondary hydroxy groups at C2, C3, and C4 were computed for methyl beta-glucoside and methyl carba-beta-glucoside. Both computations and oxidation experiments on carba-glucosides demonstrate the crucial role of the ring oxygen in the C3 regioselectivity observed during the oxidation of glucosides. Analysis of the model systems for oxidized methyl beta-glucoside shows that the C3 oxidation product is intrinsically favored in the presence of the ring oxygen. Subsequent energy decomposition analysis (EDA) and Hirschfeld charge analysis reveal the role of the ring oxygen: it positively polarizes C1/C5 by inductive effects and disfavors any subsequent buildup of positive charge at neighboring carbon atoms, rendering C3 the most favored site for the beta-hydride elimination. |
| Databáze: | OpenAIRE |
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