Characterization of elusive rhamnosyl dioxanium ions and their application in complex oligosaccharide synthesis

Peter H. Moons, Floor Braak, Frank F. J. Kleijne, Bart Bijleveld, Sybren J. R. Corver, Kas J. Houthuijs, Hero R. Almizori, Giel Berden, Jonathan Martens, Jos Oomens, Paul B. White () and Thomas J. Boltje ()
Additional contact information
Peter H. Moons: Institute for Molecules and Materials, Radboud University Nijmegen, Heyendaalseweg 135
Floor Braak: Institute for Molecules and Materials, Radboud University Nijmegen, Heyendaalseweg 135
Frank F. J. Kleijne: Institute for Molecules and Materials, Radboud University Nijmegen, Heyendaalseweg 135
Bart Bijleveld: Institute for Molecules and Materials, Radboud University Nijmegen, Heyendaalseweg 135
Sybren J. R. Corver: Institute for Molecules and Materials, Radboud University Nijmegen, Heyendaalseweg 135
Kas J. Houthuijs: Radboud University Nijmegen, Toernooiveld 7
Hero R. Almizori: Institute for Molecules and Materials, Radboud University Nijmegen, Heyendaalseweg 135
Giel Berden: Radboud University Nijmegen, Toernooiveld 7
Jonathan Martens: Radboud University Nijmegen, Toernooiveld 7
Jos Oomens: Radboud University Nijmegen, Toernooiveld 7
Paul B. White: Institute for Molecules and Materials, Radboud University Nijmegen, Heyendaalseweg 135
Thomas J. Boltje: Institute for Molecules and Materials, Radboud University Nijmegen, Heyendaalseweg 135

Nature Communications, 2024, vol. 15, issue 1, 1-13

Abstract: Abstract Attaining complete anomeric control is still one of the biggest challenges in carbohydrate chemistry. Glycosyl cations such as oxocarbenium and dioxanium ions are key intermediates of glycosylation reactions. Characterizing these highly-reactive intermediates and understanding their glycosylation mechanisms are essential to the stereoselective synthesis of complex carbohydrates. Although C-2 acyl neighbouring-group participation has been well-studied, the reactive intermediates in more remote participation remain elusive and are challenging to study. Herein, we report a workflow that is utilized to characterize rhamnosyl 1,3-bridged dioxanium ions derived from C-3 p-anisoyl esterified donors. First, we use a combination of quantum-chemical calculations and infrared ion spectroscopy to determine the structure of the cationic glycosylation intermediate in the gas-phase. In addition, we establish the structure and exchange kinetics of highly-reactive, low-abundance species in the solution-phase using chemical exchange saturation transfer, exchange spectroscopy, correlation spectroscopy, heteronuclear single-quantum correlation, and heteronuclear multiple-bond correlation nuclear magnetic resonance spectroscopy. Finally, we apply C-3 acyl neighbouring-group participation to the synthesis of complex bacterial oligosaccharides. This combined approach of finding answers to fundamental physical-chemical questions and their application in organic synthesis provides a robust basis for elucidating highly-reactive intermediates in glycosylation reactions.

Date: 2024
References: View references in EconPapers View complete reference list from CitEc
Citations:

Downloads: (external link)
https://www.nature.com/articles/s41467-024-46522-2 Abstract (text/html)

Related works:
This item may be available elsewhere in EconPapers: Search for items with the same title.

Export reference: BibTeX RIS (EndNote, ProCite, RefMan) HTML/Text

Persistent link: https://EconPapers.repec.org/RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-46522-2

Ordering information: This journal article can be ordered from
https://www.nature.com/ncomms/

DOI: 10.1038/s41467-024-46522-2

Access Statistics for this article

Nature Communications is currently edited by Nathalie Le Bot, Enda Bergin and Fiona Gillespie

More articles in Nature Communications from Nature
Bibliographic data for series maintained by Sonal Shukla () and Springer Nature Abstracting and Indexing ().