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

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

Authors :
Elferink H
Remmerswaal WA
Houthuijs KJ
Jansen O
Hansen T
Rijs AM
Berden G
Martens J
Oomens J
Codée JDC
Boltje TJ
Source :
Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2022 Nov 11; Vol. 28 (63), pp. e202201724. Date of Electronic Publication: 2022 Sep 12.
Publication Year :
2022

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.<br /> (© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Details

Language :
English
ISSN :
1521-3765
Volume :
28
Issue :
63
Database :
MEDLINE
Journal :
Chemistry (Weinheim an der Bergstrasse, Germany)
Publication Type :
Academic Journal
Accession number :
35959853
Full Text :
https://doi.org/10.1002/chem.202201724