Characterization of glycosyl dioxolenium ions and their role in glycosylation reactions

Thomas Hansen, Hidde Elferink, Jacob M.A. van Hengst, Kas J. Houthuijs, Wouter A. Remmerswaal, Alexandra Kromm, Giel Berden, Stefan van der Vorm, Anouk M. Rijs, Hermen S. Overkleeft, Dmitri V. Filippov, Floris P.J.T. Rutjes, Gijsbert A. van der Marel, Jonathan Martens, Jos Oomens, Jeroen D.C. Codée*, Thomas J. Boltje

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

Controlling the chemical glycosylation reaction remains the major challenge in the synthesis of oligosaccharides. Though 1,2-trans glycosidic linkages can be installed using neighboring group participation, the construction of 1,2-cis linkages is difficult and has no general solution. Long-range participation (LRP) by distal acyl groups may steer the stereoselectivity, but contradictory results have been reported on the role and strength of this stereoelectronic effect. It has been exceedingly difficult to study the bridging dioxolenium ion intermediates because of their high reactivity and fleeting nature. Here we report an integrated approach, using infrared ion spectroscopy, DFT computations, and a systematic series of glycosylation reactions to probe these ions in detail. Our study reveals how distal acyl groups can play a decisive role in shaping the stereochemical outcome of a glycosylation reaction, and opens new avenues to exploit these species in the assembly of oligosaccharides and glycoconjugates to fuel biological research.

Original languageEnglish
Article number2664
JournalNature Communications
Volume11
Issue number1
DOIs
Publication statusPublished - 1 Dec 2020

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