The Glycosylation Mechanisms of 6,3-Uronic Acid Lactones

Hidde Elferink, Rens A. Mensink, Wilke W.A. Castelijns, Oscar Jansen, Jeroen P.J. Bruekers, Jonathan Martens, Jos Oomens, Anouk M. Rijs*, Thomas J. Boltje

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review


Uronic acids are important constituents of polysaccharides found on the cell membranes of different organisms. To prepare uronic-acid-containing oligosaccharides, uronic acid 6,3-lactones can be employed as they display a fixed conformation and a unique reactivity and stereoselectivity. Herein, we report a highly β-selective and efficient mannosyl donor based on C-4 acetyl mannuronic acid 6,3-lactone donors. The mechanism of glycosylation is established using a combination of techniques, including infrared ion spectroscopy combined with quantum-chemical calculations and variable-temperature nuclear magnetic resonance (VT NMR) spectroscopy. The role of these intermediates in glycosylation is assayed by varying the activation protocol and acceptor nucleophilicity. The observed trends are analogous to the well-studied 4,6-benzylidene glycosides and may be used to guide the development of next-generation stereoselective glycosyl donors.

Original languageEnglish
Pages (from-to)8746-8751
Number of pages6
JournalAngewandte Chemie - International Edition
Issue number26
Publication statusPublished - 24 Jun 2019
Externally publishedYes


We would like to acknowledge Dr. P. B. White for his help with the VT NMR experiments and Dr. G. Berden for his support with the IR-MS experiments. We gratefully acknowledge the Nederlandse Organisatie voor Wetenschappelijk Onderzoek (NWO) for the support of the FELIX Laboratory. Calculations were carried out at the SurfSARA Cartesius cluster under NWO Rekentijd contract 16327. This work was supported by a ERC-STG (758913) grant awarded to T.J.B.

FundersFunder number
NWO Rekentijd16327
Horizon 2020 Framework Programme758913
Nederlandse Organisatie voor Wetenschappelijk Onderzoek


    • glycosylation
    • infrared ion spectroscopy
    • NMR spectroscopy
    • oxocarbenium ion
    • uronic acids


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