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

MPS-Authors
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Mucha,  Eike
Molecular Physics, Fritz Haber Institute, Max Planck Society;
Institute of Chemistry and Biochemistry, Freie Universität Berlin;

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Marianski,  Mateusz
Molecular Physics, Fritz Haber Institute, Max Planck Society;
Hunter College, The City University of New York;

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Thomas,  Daniel
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Meijer,  Gerard
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Helden,  Gert von
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Pagel,  Kevin
Molecular Physics, Fritz Haber Institute, Max Planck Society;
Institute of Chemistry and Biochemistry, Freie Universität Berlin;

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Fulltext (public)

s41467-018-06764-3.pdf
(Publisher version), 588KB

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Citation

Mucha, E., Marianski, M., Xu, F.-F., Thomas, D., Meijer, G., Helden, G. v., et al. (2018). Unravelling the structure of glycosyl cations via cold-ion infrared spectroscopy. Nature Communications, 9: 4174. doi:10.1038/s41467-018-06764-3.


Cite as: http://hdl.handle.net/21.11116/0000-0002-5344-4
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.