On the Origin of Regioselectivity in Palladium-Catalyzed Oxidation of Glucosides

Ieng Chim Wan; Trevor A. Hamlin; Niek N.H.M. Eisink; Nittert Marinus; Casper de Boer; Christopher A. Vis; Jeroen D. C. Codée; Martin D. Witte; Adriaan J. Minnaard; F. Matthias Bickelhaupt

doi:10.1002/ejoc.202001453

On the Origin of Regioselectivity in Palladium-Catalyzed Oxidation of Glucosides

Ieng Chim Wan, Trevor A. Hamlin, Niek N.H.M. Eisink, Nittert Marinus, Casper de Boer, Christopher A. Vis, Jeroen D. C. Codée, Martin D. Witte^*, Adriaan J. Minnaard, F. Matthias Bickelhaupt

^*Corresponding author for this work

Chemical Biology 2

Research output: Contribution to journal › Article › Academic › peer-review

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Abstract

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 β-glucoside and methyl carba-β-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 β-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 β-hydride elimination.

Original language	English
Pages (from-to)	632-636
Number of pages	5
Journal	European Journal of Organic Chemistry
Volume	2021
Issue number	4
DOIs	https://doi.org/10.1002/ejoc.202001453
Publication status	Published - 26-Jan-2021

Keywords

Carbohydrates
Density functional calculations
Energy decomposition analysis
Oxidation
Regioselectivity

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On the Origin of Regioselectivity in Palladium-Catalyzed Oxidation of GlucosidesFinal publisher's version, 1.04 MBLicence: CC BY

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Wan, Ieng Chim ; Hamlin, Trevor A. ; Eisink, Niek N.H.M. ; Marinus, Nittert ; de Boer, Casper ; Vis, Christopher A. ; Codée, Jeroen D. C. ; Witte, Martin D. ; Minnaard, Adriaan J. ; Bickelhaupt, F. Matthias. / On the Origin of Regioselectivity in Palladium-Catalyzed Oxidation of Glucosides. In: European Journal of Organic Chemistry. 2021 ; Vol. 2021, No. 4. pp. 632-636.

@article{59b4a08593874339ba2dae9174a5cec6,

title = "On the Origin of Regioselectivity in Palladium-Catalyzed Oxidation of Glucosides",

abstract = "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 β-glucoside and methyl carba-β-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 β-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 β-hydride elimination.",

keywords = "Carbohydrates, Density functional calculations, Energy decomposition analysis, Oxidation, Regioselectivity",

author = "Wan, {Ieng Chim} and Hamlin, {Trevor A.} and Eisink, {Niek N.H.M.} and Nittert Marinus and {de Boer}, Casper and Vis, {Christopher A.} and Cod{\'e}e, {Jeroen D. C.} and Witte, {Martin D.} and Minnaard, {Adriaan J.} and Bickelhaupt, {F. Matthias}",

note = "Funding Information: We thank the Netherlands Organization for Scientific Research (NWO) for financial support. Publisher Copyright: {\textcopyright} 2020 The Authors. European Journal of Organic Chemistry published by Wiley-VCH GmbH Copyright: Copyright 2021 Elsevier B.V., All rights reserved.",

year = "2021",

month = jan,

day = "26",

doi = "10.1002/ejoc.202001453",

language = "English",

volume = "2021",

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journal = "European Journal of Organic Chemistry",

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On the Origin of Regioselectivity in Palladium-Catalyzed Oxidation of Glucosides. / Wan, Ieng Chim; Hamlin, Trevor A.; Eisink, Niek N.H.M.; Marinus, Nittert; de Boer, Casper; Vis, Christopher A.; Codée, Jeroen D. C.; Witte, Martin D.; Minnaard, Adriaan J.; Bickelhaupt, F. Matthias.

In: European Journal of Organic Chemistry, Vol. 2021, No. 4, 26.01.2021, p. 632-636.

Research output: Contribution to journal › Article › Academic › peer-review

TY - JOUR

T1 - On the Origin of Regioselectivity in Palladium-Catalyzed Oxidation of Glucosides

AU - Wan, Ieng Chim

AU - Hamlin, Trevor A.

AU - Eisink, Niek N.H.M.

AU - Marinus, Nittert

AU - de Boer, Casper

AU - Vis, Christopher A.

AU - Codée, Jeroen D. C.

AU - Witte, Martin D.

AU - Minnaard, Adriaan J.

AU - Bickelhaupt, F. Matthias

N1 - Funding Information: We thank the Netherlands Organization for Scientific Research (NWO) for financial support. Publisher Copyright: © 2020 The Authors. European Journal of Organic Chemistry published by Wiley-VCH GmbH Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2021/1/26

Y1 - 2021/1/26

N2 - 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 β-glucoside and methyl carba-β-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 β-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 β-hydride elimination.

AB - 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 β-glucoside and methyl carba-β-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 β-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 β-hydride elimination.

KW - Carbohydrates

KW - Density functional calculations

KW - Energy decomposition analysis

KW - Oxidation

KW - Regioselectivity

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U2 - 10.1002/ejoc.202001453

DO - 10.1002/ejoc.202001453

M3 - Article

AN - SCOPUS:85099174845

VL - 2021

SP - 632

EP - 636

JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

SN - 1434-193X

IS - 4

ER -

On the Origin of Regioselectivity in Palladium-Catalyzed Oxidation of Glucosides

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