| Autor: |
Adero PO; Department of Chemistry , Wayne State University , 5101 Cass Avenue , Detroit , Michigan 48202 , United States., Amarasekara H; Department of Chemistry , Wayne State University , 5101 Cass Avenue , Detroit , Michigan 48202 , United States., Wen P; Department of Chemistry , Wayne State University , 5101 Cass Avenue , Detroit , Michigan 48202 , United States., Bohé L; Institut de Chimie des Substances Naturelles, CNRS UPR 2301 , Université Paris-Sud Université Paris-Saclay , 1 avenue de la Terrasse , 91198 Gif-sur-Yvette , France., Crich D; Department of Chemistry , Wayne State University , 5101 Cass Avenue , Detroit , Michigan 48202 , United States. |
| Abstrakt: |
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 S N 1 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. |
