The Experimental Evidence in Support of Glycosylation Mechanisms at the S1-S2 Interface

Overview

Journal Chem Rev

Publisher American Chemical Society

Specialty Chemistry

Date 2018 May 31

PMID 29846062

Citations 81

Authors

Philip Ouma Adero

Harsha Amarasekara

Peng Wen

Luis Bohe

David Crich

Affiliations

Soon will be listed here.

Abstract

A critical review of the state-of-the-art evidence in support of the mechanisms of glycosylation reactions is provided. Factors affecting the stability of putative oxocarbenium ions as intermediates at the S1 end of the mechanistic continuum are first surveyed before the evidence, spectroscopic and indirect, for the existence of such species on the time scale of glycosylation reactions is presented. Current models for diastereoselectivity in nucleophilic attack on oxocarbenium ions are then described. Evidence in support of the intermediacy of activated covalent glycosyl donors is reviewed, before the influences of the structure of the nucleophile, of the solvent, of temperature, and of donor-acceptor hydrogen bonding on the mechanism of glycosylation reactions are surveyed. Studies on the kinetics of glycosylation reactions and the use of kinetic isotope effects for the determination of transition-state structure are presented, before computational models are finally surveyed. The review concludes with a critical appraisal of the state of the art.

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