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

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 languageEnglish
Pages (from-to)8746-8751
Number of pages6
JournalAngewandte Chemie - International Edition
Volume58
Issue number26
DOIs
Publication statusPublished - 24 Jun 2019
Externally publishedYes

Keywords

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

Fingerprint

Dive into the research topics of 'The Glycosylation Mechanisms of 6,3-Uronic Acid Lactones'. Together they form a unique fingerprint.

Cite this