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

doi:10.1002/anie.201902507

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 Journal › Article › Academic › peer-review

Abstract

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 language	English
Pages (from-to)	8746-8751
Number of pages	6
Journal	Angewandte Chemie - International Edition
Volume	58
Issue number	26
DOIs	https://doi.org/10.1002/anie.201902507
Publication status	Published - 24 Jun 2019
Externally published	Yes

Funding

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.

Funders	Funder number
ERC-StG
NWO Rekentijd	16327
Horizon 2020 Framework Programme	758913
Nederlandse Organisatie voor Wetenschappelijk Onderzoek

Keywords

glycosylation
infrared ion spectroscopy
NMR spectroscopy
oxocarbenium ion
uronic acids

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title = "The Glycosylation Mechanisms of 6,3-Uronic Acid Lactones",

abstract = "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.",

keywords = "glycosylation, infrared ion spectroscopy, NMR spectroscopy, oxocarbenium ion, uronic acids",

author = "Hidde Elferink and Mensink, {Rens A.} and Castelijns, {Wilke W.A.} and Oscar Jansen and Bruekers, {Jeroen P.J.} and Jonathan Martens and Jos Oomens and Rijs, {Anouk M.} and Boltje, {Thomas J.}",

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AU - Mensink, Rens A.

AU - Castelijns, Wilke W.A.

AU - Jansen, Oscar

AU - Bruekers, Jeroen P.J.

AU - Martens, Jonathan

AU - Oomens, Jos

AU - Rijs, Anouk M.

AU - Boltje, Thomas J.

PY - 2019/6/24

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N2 - 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.

AB - 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.

KW - glycosylation

KW - infrared ion spectroscopy

KW - NMR spectroscopy

KW - oxocarbenium ion

KW - uronic acids

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The Glycosylation Mechanisms of 6,3-Uronic Acid Lactones

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