Characterization of Glycosyl Dioxolenium Ions and Their Role in Glycosylation Reactions

Overview

Journal Nat Commun

Specialty Biology

Date 2020 May 31

PMID 32471982

Citations 40

Authors

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 Codee

Thomas J Boltje

Affiliations

Soon will be listed here.

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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