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Unravelling the structure of glycosyl cations via cold-ion infrared spectroscopy

Author

Listed:
  • Eike Mucha

    (Fritz Haber Institute of the Max Planck Society
    Freie Universität Berlin)

  • Mateusz Marianski

    (Fritz Haber Institute of the Max Planck Society
    The City University of New York)

  • Fei-Fei Xu

    (Max Planck Institute of Colloids and Interfaces)

  • Daniel A. Thomas

    (Fritz Haber Institute of the Max Planck Society)

  • Gerard Meijer

    (Fritz Haber Institute of the Max Planck Society)

  • Gert von Helden

    (Fritz Haber Institute of the Max Planck Society)

  • Peter H. Seeberger

    (Freie Universität Berlin
    Max Planck Institute of Colloids and Interfaces)

  • Kevin Pagel

    (Fritz Haber Institute of the Max Planck Society
    Freie Universität Berlin)

Abstract

Glycosyl cations are the key intermediates during the glycosylation reaction that covalently links building blocks during the synthetic assembly of carbohydrates. The exact structure of these ions remained elusive due to their transient and short-lived nature. Structural insights into the intermediate would improve our understanding of the reaction mechanism of glycosidic bond formation. Here, we report an in-depth structural analysis of glycosyl cations using a combination of cold-ion infrared spectroscopy and first-principles theory. Participating C2 protective groups form indeed a covalent bond with the anomeric carbon that leads to C1-bridged acetoxonium-type structures. The resulting bicyclic structure strongly distorts the ring, which leads to a unique conformation for each individual monosaccharide. This gain in mechanistic understanding fundamentally impacts glycosynthesis and will allow to tailor building blocks and reaction conditions in the future.

Suggested Citation

  • Eike Mucha & Mateusz Marianski & Fei-Fei Xu & Daniel A. Thomas & Gerard Meijer & Gert von Helden & Peter H. Seeberger & Kevin Pagel, 2018. "Unravelling the structure of glycosyl cations via cold-ion infrared spectroscopy," Nature Communications, Nature, vol. 9(1), pages 1-5, December.
    • Handle: RePEc:nat:natcom:v:9:y:2018:i:1:d:10.1038_s41467-018-06764-3
    DOI: 10.1038/s41467-018-06764-3
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    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.

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