Competing C-4 and C-5-Acyl Stabilization of Uronic Acid Glycosyl Cations

Hidde Elferink; Wouter A. Remmerswaal; Kas J. Houthuijs; Oscar Jansen; Thomas Hansen; Anouk M. Rijs; Giel Berden; Jonathan Martens; Jos Oomens; Jeroen D.C. Codée; Thomas J. Boltje

doi:10.1002/chem.202201724

Competing C-4 and C-5-Acyl Stabilization of Uronic Acid Glycosyl Cations

Hidde Elferink, Wouter A. Remmerswaal, Kas J. Houthuijs, Oscar Jansen, Thomas Hansen, Anouk M. Rijs, Giel Berden, Jonathan Martens, Jos Oomens, Jeroen D.C. Codée, Thomas J. Boltje^*

^*Corresponding author for this work

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

Abstract

Uronic acids are carbohydrates carrying a terminal carboxylic acid and have a unique reactivity in stereoselective glycosylation reactions. Herein, the competing intramolecular stabilization of uronic acid cations by the C-5 carboxylic acid or the C-4 acetyl group was studied with infrared ion spectroscopy (IRIS). IRIS reveals that a mixture of bridged ions is formed, in which the mixture is driven towards the C-1,C-5 dioxolanium ion when the C-5,C-2-relationship is cis, and towards the formation of the C-1,C-4 dioxepanium ion when this relation is trans. Isomer-population analysis and interconversion barrier computations show that the two bridged structures are not in dynamic equilibrium and that their ratio parallels the density functional theory computed stability of the structures. These studies reveal how the intrinsic interplay of the different functional groups influences the formation of the different regioisomeric products.

Original language	English
Article number	e202201724
Pages (from-to)	1-8
Number of pages	8
Journal	Chemistry - A European Journal
Volume	28
Issue number	63
Early online date	12 Aug 2022
DOIs	https://doi.org/10.1002/chem.202201724
Publication status	Published - 11 Nov 2022

Bibliographical note

Funding Information:
This work was supported by the Nederlandse Organisatie voor Wetenschappelijk Onderzoek (NWO‐VICI grant VI.C.182.020 to JDCC, NWO‐VIDI grant VI.Vidi.192.070 awarded to TJB and the research program “National Roadmap Grootschalige Wetenschappelijke Infastructuur” 184.034.022 awarded to HFML‐FELIX) and SURFsara for computational resources [NWO Rekentijd Grant 2021.055 awarded to JO, NWO Rekentijd Grant 2021/ENW/01070753 awarded to JDCC].

Publisher Copyright:
© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.

Funding

This work was supported by the Nederlandse Organisatie voor Wetenschappelijk Onderzoek (NWO‐VICI grant VI.C.182.020 to JDCC, NWO‐VIDI grant VI.Vidi.192.070 awarded to TJB and the research program “National Roadmap Grootschalige Wetenschappelijke Infastructuur” 184.034.022 awarded to HFML‐FELIX) and SURFsara for computational resources [NWO Rekentijd Grant 2021.055 awarded to JO, NWO Rekentijd Grant 2021/ENW/01070753 awarded to JDCC].

Funders	Funder number
NWO-VICI
NWO-VIDI	VI.Vidi.192.070, 2021/ENW/01070753, 184.034.022, 2021.055
UK Research and Innovation	25397
NWO‐VICI	VI.C.182.020

Keywords

carbohydrates
computational chemistry
IR spectroscopy
reaction mechanisms

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10.1002/chem.202201724

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Cite this

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title = "Competing C-4 and C-5-Acyl Stabilization of Uronic Acid Glycosyl Cations",

abstract = "Uronic acids are carbohydrates carrying a terminal carboxylic acid and have a unique reactivity in stereoselective glycosylation reactions. Herein, the competing intramolecular stabilization of uronic acid cations by the C-5 carboxylic acid or the C-4 acetyl group was studied with infrared ion spectroscopy (IRIS). IRIS reveals that a mixture of bridged ions is formed, in which the mixture is driven towards the C-1,C-5 dioxolanium ion when the C-5,C-2-relationship is cis, and towards the formation of the C-1,C-4 dioxepanium ion when this relation is trans. Isomer-population analysis and interconversion barrier computations show that the two bridged structures are not in dynamic equilibrium and that their ratio parallels the density functional theory computed stability of the structures. These studies reveal how the intrinsic interplay of the different functional groups influences the formation of the different regioisomeric products.",

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note = "Funding Information: This work was supported by the Nederlandse Organisatie voor Wetenschappelijk Onderzoek (NWO‐VICI grant VI.C.182.020 to JDCC, NWO‐VIDI grant VI.Vidi.192.070 awarded to TJB and the research program “National Roadmap Grootschalige Wetenschappelijke Infastructuur” 184.034.022 awarded to HFML‐FELIX) and SURFsara for computational resources [NWO Rekentijd Grant 2021.055 awarded to JO, NWO Rekentijd Grant 2021/ENW/01070753 awarded to JDCC]. Publisher Copyright: {\textcopyright} 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.",

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AU - Jansen, Oscar

AU - Hansen, Thomas

AU - Rijs, Anouk M.

AU - Berden, Giel

AU - Martens, Jonathan

AU - Oomens, Jos

AU - Codée, Jeroen D.C.

AU - Boltje, Thomas J.

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PY - 2022/11/11

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Competing C-4 and C-5-Acyl Stabilization of Uronic Acid Glycosyl Cations

Abstract

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Keywords

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