Abstract
Glycosyl cations are universally accepted key ionic intermediates in the mechanism of glycosylation, the reaction that covalently links carbohydrates to other molecules. These ions have remained hypothetical species so far because of their extremely short life in organic media as a consequence of their very high reactivity. Here, we report the use of liquid hydrofluoric acid–antimony pentafluoride (HF/SbF5) superacid to generate and stabilize the glycosyl cations derived from peracetylated 2-deoxy and 2-bromoglucopyranose in a condensed phase. Their persistence in this superacid medium allows their three-dimensional structure to be studied by NMR, aided by complementary computations. Their deuteration further confirms the impact of the structure of the glycosyl cation on the stereochemical outcome of its trapping.
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Acknowledgements
A.M. acknowledges the Agence Nationale de la Recherche (ANR) for a PhD grant (project ANR-12-BS07-0003-01). N.P. acknowledges the Foundation for the Development of the Chemistry of Natural Products of the French Academy of Sciences for a post-doctoral fellowship. J.D., A.M.-M., S.T. and Y.B. acknowledge the French Centre National de la Recherche Scientifique, (PICS program), the ANR (project ANR-12-BS07-0003-01), the Regional Council Poitou-Charentes and the University of Poitiers for financial support. A.A. and J.J.-B. acknowledge the Centro de Supercomputación de Galicia (CESGA) for computational resources and the Ministery of Economy and Competitiveness of Spain for funding (project CTQ2012-32025).
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Y.B. and P.S. initiated the study. Y.B. and S.T. designed the study. A.M., N.P. and J.D. synthesized the sugar precursors. A.M., A.M.M. and N.P. performed the superacid experiments. A.M., A.M.M., J.D., S.T., Y.B., J.J.-B. and A.A. analysed the NMR spectra. J.J.-B. and A.A. performed the computation. Y.B., J.J.B. and S.T. wrote the paper. All authors discussed the results and commented on the manuscript.
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Martin, A., Arda, A., Désiré, J. et al. Catching elusive glycosyl cations in a condensed phase with HF/SbF5 superacid. Nature Chem 8, 186–191 (2016). https://doi.org/10.1038/nchem.2399
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DOI: https://doi.org/10.1038/nchem.2399
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