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Vrande, K.N.A. van de (2025)

Unravelling glycosylation reaction mechanisms

Doctoral Thesis
A key step in the synthesis of oligosaccharides and glycoconjugates is the formation of the glycosidic bond. The stereoselective formation of glycosidic bonds, however, can be difficult and whereas 1,2-trans bonds can easily be formed by the participation of the protective group on the C-2 position, no general methodology exists for the synthesis of 1,2-cis glycosidic bonds. Furthermore, the formation of these bonds does not take place via a clear-cut single-reaction mechanism. Instead, the mechanism that is followed lies somewhere on the spectrum between the SN1 and SN2 reaction mechanisms, involving different reactive intermediates, ranging from covalent ones to ion pairs. These, in combination with the reactivity of the incoming nucleophile, play a crucial role in shaping the outcome of a glycosylation reaction. The aim of this thesis is to study glycosylation reaction mechanisms in a systematic manner by making use of physical-chemical techniques that often rely on isotopic...Show moreA key step in the synthesis of oligosaccharides and glycoconjugates is the formation of the glycosidic bond. The stereoselective formation of glycosidic bonds, however, can be difficult and whereas 1,2-trans bonds can easily be formed by the participation of the protective group on the C-2 position, no general methodology exists for the synthesis of 1,2-cis glycosidic bonds. Furthermore, the formation of these bonds does not take place via a clear-cut single-reaction mechanism. Instead, the mechanism that is followed lies somewhere on the spectrum between the SN1 and SN2 reaction mechanisms, involving different reactive intermediates, ranging from covalent ones to ion pairs. These, in combination with the reactivity of the incoming nucleophile, play a crucial role in shaping the outcome of a glycosylation reaction. The aim of this thesis is to study glycosylation reaction mechanisms in a systematic manner by making use of physical-chemical techniques that often rely on isotopic labelling.
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Glycosylation Reactions
Kinetic Isotope Effects
Reaction Mechanisms
Isotopic Labelling
All authors
Vrande, K.N.A. van de
Supervisor
Codée, J.D.C.; Filippov, D.V.
Committee
Ubbink, M.; Overkleeft, H.S.; Vorm, S. van der; Galan, M.C.; Hansen, T.
Qualification
Doctor (dr.)
Awarding Institution
Leiden Institute of Chemistry (LIC), Faculty of Science, Leiden University
Date
2025-10-09
ISBN (print)
9789465223841