IDEAS home Printed from https://ideas.repec.org/a/nat/natcom/v11y2020i1d10.1038_s41467-020-16362-x.html
   My bibliography  Save this article

Characterization of glycosyl dioxolenium ions and their role in glycosylation reactions

Author

Listed:
  • Thomas Hansen

    (Leiden University, Leiden Institute of Chemistry)

  • Hidde Elferink

    (Radboud University Institute for Molecules and Materials)

  • Jacob M. A. Hengst

    (Leiden University, Leiden Institute of Chemistry)

  • Kas J. Houthuijs

    (Radboud University Institute for Molecules and Materials)

  • Wouter A. Remmerswaal

    (Leiden University, Leiden Institute of Chemistry)

  • Alexandra Kromm

    (Radboud University Institute for Molecules and Materials)

  • Giel Berden

    (Radboud University Institute for Molecules and Materials, FELIX Laboratory, Toernooiveld 7-c)

  • Stefan Vorm

    (Leiden University, Leiden Institute of Chemistry)

  • Anouk M. Rijs

    (Radboud University Institute for Molecules and Materials, FELIX Laboratory, Toernooiveld 7-c)

  • Hermen S. Overkleeft

    (Leiden University, Leiden Institute of Chemistry)

  • Dmitri V. Filippov

    (Leiden University, Leiden Institute of Chemistry)

  • Floris P. J. T. Rutjes

    (Radboud University Institute for Molecules and Materials)

  • Gijsbert A. Marel

    (Leiden University, Leiden Institute of Chemistry)

  • Jonathan Martens

    (Radboud University Institute for Molecules and Materials, FELIX Laboratory, Toernooiveld 7-c)

  • Jos Oomens

    (Radboud University Institute for Molecules and Materials, FELIX Laboratory, Toernooiveld 7-c)

  • Jeroen D. C. Codée

    (Leiden University, Leiden Institute of Chemistry)

  • Thomas J. Boltje

    (Radboud University Institute for Molecules and Materials)

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.

Suggested Citation

  • Thomas Hansen & Hidde Elferink & Jacob M. A. Hengst & Kas J. Houthuijs & Wouter A. Remmerswaal & Alexandra Kromm & Giel Berden & Stefan Vorm & Anouk M. Rijs & Hermen S. Overkleeft & Dmitri V. Filippov, 2020. "Characterization of glycosyl dioxolenium ions and their role in glycosylation reactions," Nature Communications, Nature, vol. 11(1), pages 1-9, December.
    • Handle: RePEc:nat:natcom:v:11:y:2020:i:1:d:10.1038_s41467-020-16362-x
    DOI: 10.1038/s41467-020-16362-x
    as

    Download full text from publisher

    File URL: https://www.nature.com/articles/s41467-020-16362-x
    File Function: Abstract
    Download Restriction: no
    File URL: https://libkey.io/10.1038/s41467-020-16362-x?utm_source=ideas
    LibKey link: if access is restricted and if your library uses this service, LibKey will redirect you to where you can use your library subscription to access this item
    ---><---

    Citations

    Citations are extracted by the CitEc Project, subscribe to its RSS feed for this item.
    as


    Cited by:

    1. 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 & Thomas J, 2024. "Characterization of elusive rhamnosyl dioxanium ions and their application in complex oligosaccharide synthesis," Nature Communications, Nature, vol. 15(1), pages 1-13, December.

    More about this item

    Statistics

    Access and download statistics

    Corrections

    All material on this site has been provided by the respective publishers and authors. You can help correct errors and omissions. When requesting a correction, please mention this item's handle: RePEc:nat:natcom:v:11:y:2020:i:1:d:10.1038_s41467-020-16362-x. See general information about how to correct material in RePEc.

    If you have authored this item and are not yet registered with RePEc, we encourage you to do it here. This allows to link your profile to this item. It also allows you to accept potential citations to this item that we are uncertain about.

    We have no bibliographic references for this item. You can help adding them by using this form .

    If you know of missing items citing this one, you can help us creating those links by adding the relevant references in the same way as above, for each refering item. If you are a registered author of this item, you may also want to check the "citations" tab in your RePEc Author Service profile, as there may be some citations waiting for confirmation.

    For technical questions regarding this item, or to correct its authors, title, abstract, bibliographic or download information, contact: Sonal Shukla or Springer Nature Abstracting and Indexing (email available below). General contact details of provider: http://www.nature.com .

    Please note that corrections may take a couple of weeks to filter through the various RePEc services.

    IDEAS is a RePEc service. RePEc uses bibliographic data supplied by the respective publishers.