Defining the S1 Side of Glycosylation Reactions: Stereoselectivity of Glycopyranosyl Cations

Overview

Journal ACS Cent Sci

Specialty Chemistry

Date 2019 May 30

PMID 31139714

Citations 29

Authors

Thomas Hansen

Ludivine Lebedel

Wouter A Remmerswaal

Stefan van der Vorm

Dennis P A Wander

Mark Somers

Herman S Overkleeft

Dmitri V Filippov

Jerome Desire

Agnes Mingot

Yves Bleriot

Gijsbert A van der Marel

Sebastien Thibaudeau

Jeroen D C Codee

Affiliations

Soon will be listed here.

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 S1-type glycosylation reactions firmly establishes glycosyl cations as true reaction intermediates and will enable the generation of new stereoselective glycosylation methodology.

Citing Articles

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