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*

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-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 SN1-type glycosylation reactions firmly establishes glycosyl cations as true reaction intermediates and will enable the generation of new stereoselective glycosylation methodology.

Original languageEnglish
Pages (from-to)781-788
Number of pages8
JournalACS Central Science
Volume5
Issue number5
DOIs
Publication statusPublished - 22 May 2019

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