Characterization of glycosyl dioxolenium ions and their role in glycosylation reactions

Thomas Hansen; Hidde Elferink; Jacob M.A. van Hengst; Kas J. Houthuijs; Wouter A. Remmerswaal; Alexandra Kromm; Giel Berden; Stefan van der Vorm; Anouk M. Rijs; Hermen S. Overkleeft; Dmitri V. Filippov; Floris P.J.T. Rutjes; Gijsbert A. van der Marel; Jonathan Martens; Jos Oomens; Jeroen D.C. Codée; Thomas J. Boltje

doi:10.1038/s41467-020-16362-x

Characterization of glycosyl dioxolenium ions and their role in glycosylation reactions

Thomas Hansen, Hidde Elferink, Jacob M.A. van Hengst, Kas J. Houthuijs, Wouter A. Remmerswaal, Alexandra Kromm, Giel Berden, Stefan van der Vorm, Anouk M. Rijs, Hermen S. Overkleeft, Dmitri V. Filippov, Floris P.J.T. Rutjes, Gijsbert A. van der Marel, Jonathan Martens, Jos Oomens, Jeroen D.C. Codée^*, Thomas J. Boltje

^*Corresponding author for this work

Research output: Contribution to Journal › Article › Academic › peer-review

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.

Original language	English
Article number	2664
Journal	Nature Communications
Volume	11
Issue number	1
DOIs	https://doi.org/10.1038/s41467-020-16362-x
Publication status	Published - 1 Dec 2020

Funding

We gratefully acknowledge the expert technical support by the FELIX staff. Quantum-chemical calculations were performed at the SurfSARA HPC center in Amsterdam; access was provided via NWO-Rekentijd grant 17603 (to J.O.) and 17569 (to T.H. and J.D.C.C.). This work was supported by an ERC‐STG (758913) and NWO VIDI grant awarded to T.J.B. and an ERC-CoG (726072) and NWO VICI (VI.C.182.020) grant awarded to J.D.C.C. We kindly acknowledge Mark Somers for technical support.

Funders	Funder number
ERC-Cog	726072
ERC‐STG
Horizon 2020 Framework Programme	758913
Nederlandse Organisatie voor Wetenschappelijk Onderzoek

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Hansen, T., Elferink, H., van Hengst, J. M. A., Houthuijs, K. J., Remmerswaal, W. A., Kromm, A., Berden, G., van der Vorm, S., Rijs, A. M., Overkleeft, H. S., Filippov, D. V., Rutjes, F. P. J. T., van der Marel, G. A., Martens, J., Oomens, J., Codée, J. D. C., & Boltje, T. J. (2020). Characterization of glycosyl dioxolenium ions and their role in glycosylation reactions. Nature Communications, 11(1), Article 2664. https://doi.org/10.1038/s41467-020-16362-x

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title = "Characterization of glycosyl dioxolenium ions and their role in glycosylation reactions",

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.",

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Hansen, T, Elferink, H, van Hengst, JMA, Houthuijs, KJ, Remmerswaal, WA, Kromm, A, Berden, G, van der Vorm, S, Rijs, AM, Overkleeft, HS, Filippov, DV, Rutjes, FPJT, van der Marel, GA, Martens, J, Oomens, J, Codée, JDC & Boltje, TJ 2020, 'Characterization of glycosyl dioxolenium ions and their role in glycosylation reactions', Nature Communications, vol. 11, no. 1, 2664. https://doi.org/10.1038/s41467-020-16362-x

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AU - Hansen, Thomas

AU - Elferink, Hidde

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AU - Remmerswaal, Wouter A.

AU - Kromm, Alexandra

AU - Berden, Giel

AU - van der Vorm, Stefan

AU - Rijs, Anouk M.

AU - Overkleeft, Hermen S.

AU - Filippov, Dmitri V.

AU - Rutjes, Floris P.J.T.

AU - van der Marel, Gijsbert A.

AU - Martens, Jonathan

AU - Oomens, Jos

AU - Codée, Jeroen D.C.

AU - Boltje, Thomas J.

PY - 2020/12/1

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Characterization of glycosyl dioxolenium ions and their role in glycosylation reactions

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Funding

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