2014 Volume 26 Issue 147 Pages 11-27
The glycosylation reaction, which makes glycosidic linkages to develop a sugar chain, is one of the essential reactions in the realms of glycoscience. An understanding of mechanistic details of this key reaction will not only give researchers deeper insights on the nature of biochemical glycosylation reactions but will further the development of synthetic strategies in a rational way. In the present article we will overview the studies on mechanisms of glycosylation reactions, focusing on those using computational approaches. We review theoretical studies on general mechanistic issues, extensively discussing them in conjunction with the influence of neighboring groups and solvents, as well as stereoelectronic effect. The influence of a glycosyl donor’s conformational flexibility on its reactivity/stereoselectivity and the debate about exocyclic or endocyclic cleavage of pyranoside rings are also described.
