Defining the SN1 Side of Glycosylation Reactions: Stereoselectivity of Glycopyranosyl Cations

Thomas Hansen; Ludivine Lebedel; Wouter A. Remmerswaal; Stefan Van Der Vorm; Dennis P.A. Wander; Mark Somers; Herman S. Overkleeft; Dmitri V. Filippov; Jérôme Désiré; Agnès Mingot; Yves Bleriot; Gijsbert A. Van Der Marel; Sebastien Thibaudeau; Jeroen D.C. Codée

doi:10.1021/acscentsci.9b00042

Defining the S_N1 Side of Glycosylation Reactions: Stereoselectivity of Glycopyranosyl Cations

Thomas Hansen, Ludivine Lebedel, Wouter A. Remmerswaal, Stefan Van Der Vorm, Dennis P.A. Wander, Mark Somers, Herman S. Overkleeft, Dmitri V. Filippov, Jérôme Désiré, Agnès Mingot, Yves Bleriot, Gijsbert A. Van Der Marel, Sebastien Thibaudeau, Jeroen D.C. Codée^*

^*Corresponding author for this work

Chemistry and Pharmaceutical Sciences

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

Abstract

The broad application of well-defined synthetic oligosaccharides in glycobiology and glycobiotechnology is largely hampered by the lack of sufficient amounts of synthetic carbohydrate specimens. Insufficient knowledge of the glycosylation reaction mechanism thwarts the routine assembly of these materials. Glycosyl cations are key reactive intermediates in the glycosylation reaction, but their high reactivity and fleeting nature have precluded the determination of clear structure-reactivity-stereoselectivity principles for these species. We report a combined experimental and computational method that connects the stereoselectivity of oxocarbenium ions to the full ensemble of conformations these species can adopt, mapped in conformational energy landscapes (CEL), in a quantitative manner. The detailed description of stereoselective S_N1-type glycosylation reactions firmly establishes glycosyl cations as true reaction intermediates and will enable the generation of new stereoselective glycosylation methodology.

Original language	English
Pages (from-to)	781-788
Number of pages	8
Journal	ACS Central Science
Volume	5
Issue number	5
DOIs	https://doi.org/10.1021/acscentsci.9b00042
Publication status	Published - 22 May 2019

Funding

Funders	Funder number
Horizon 2020 Framework Programme	726072

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10.1021/acscentsci.9b00042

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Hansen, T., Lebedel, L., Remmerswaal, W. A., Van Der Vorm, S., Wander, D. P. A., Somers, M., Overkleeft, H. S., Filippov, D. V., Désiré, J., Mingot, A., Bleriot, Y., Van Der Marel, G. A., Thibaudeau, S., & Codée, J. D. C. (2019). Defining the S_N1 Side of Glycosylation Reactions: Stereoselectivity of Glycopyranosyl Cations. ACS Central Science, 5(5), 781-788. https://doi.org/10.1021/acscentsci.9b00042

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title = "Defining the SN1 Side of Glycosylation Reactions: Stereoselectivity of Glycopyranosyl Cations",

abstract = "The broad application of well-defined synthetic oligosaccharides in glycobiology and glycobiotechnology is largely hampered by the lack of sufficient amounts of synthetic carbohydrate specimens. Insufficient knowledge of the glycosylation reaction mechanism thwarts the routine assembly of these materials. Glycosyl cations are key reactive intermediates in the glycosylation reaction, but their high reactivity and fleeting nature have precluded the determination of clear structure-reactivity-stereoselectivity principles for these species. We report a combined experimental and computational method that connects the stereoselectivity of oxocarbenium ions to the full ensemble of conformations these species can adopt, mapped in conformational energy landscapes (CEL), in a quantitative manner. The detailed description of stereoselective SN1-type glycosylation reactions firmly establishes glycosyl cations as true reaction intermediates and will enable the generation of new stereoselective glycosylation methodology.",

author = "Thomas Hansen and Ludivine Lebedel and Remmerswaal, {Wouter A.} and {Van Der Vorm}, Stefan and Wander, {Dennis P.A.} and Mark Somers and Overkleeft, {Herman S.} and Filippov, {Dmitri V.} and J{\'e}r{\^o}me D{\'e}sir{\'e} and Agn{\`e}s Mingot and Yves Bleriot and {Van Der Marel}, {Gijsbert A.} and Sebastien Thibaudeau and Cod{\'e}e, {Jeroen D.C.}",

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doi = "10.1021/acscentsci.9b00042",

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Hansen, T, Lebedel, L, Remmerswaal, WA, Van Der Vorm, S, Wander, DPA, Somers, M, Overkleeft, HS, Filippov, DV, Désiré, J, Mingot, A, Bleriot, Y, Van Der Marel, GA, Thibaudeau, S & Codée, JDC 2019, 'Defining the S_N1 Side of Glycosylation Reactions: Stereoselectivity of Glycopyranosyl Cations', ACS Central Science, vol. 5, no. 5, pp. 781-788. https://doi.org/10.1021/acscentsci.9b00042

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AU - Hansen, Thomas

AU - Lebedel, Ludivine

AU - Remmerswaal, Wouter A.

AU - Van Der Vorm, Stefan

AU - Wander, Dennis P.A.

AU - Somers, Mark

AU - Overkleeft, Herman S.

AU - Filippov, Dmitri V.

AU - Désiré, Jérôme

AU - Mingot, Agnès

AU - Bleriot, Yves

AU - Van Der Marel, Gijsbert A.

AU - Thibaudeau, Sebastien

AU - Codée, Jeroen D.C.

PY - 2019/5/22

Y1 - 2019/5/22

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AB - The broad application of well-defined synthetic oligosaccharides in glycobiology and glycobiotechnology is largely hampered by the lack of sufficient amounts of synthetic carbohydrate specimens. Insufficient knowledge of the glycosylation reaction mechanism thwarts the routine assembly of these materials. Glycosyl cations are key reactive intermediates in the glycosylation reaction, but their high reactivity and fleeting nature have precluded the determination of clear structure-reactivity-stereoselectivity principles for these species. We report a combined experimental and computational method that connects the stereoselectivity of oxocarbenium ions to the full ensemble of conformations these species can adopt, mapped in conformational energy landscapes (CEL), in a quantitative manner. The detailed description of stereoselective SN1-type glycosylation reactions firmly establishes glycosyl cations as true reaction intermediates and will enable the generation of new stereoselective glycosylation methodology.

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