Repeating glycosidic linkages of oligosaccharides can be synthesized by solid-phase methods. Glycals were attached to a polystyrene copolymer with a silyl ether bond and were activated to function as glycosyl donors with 3,3-dimethyldioxirane. Glycosidation was performed by reactions with a solution-based acceptor (itself a glycal). Excess acceptor and promoter were removed by rinsing after each coupling, and the desired oligosaccharides were then easily obtained from the polymer by the addition of tetra-n-butylammonium fluoride. By this method, glycosidations are stereospecific and interior deletions are avoided.

https://science.sciencemag.org/content/sci/260/5112/1307.full.pdf

A strategy for the solid-phase synthesis of oligosaccharides

The highly stereoselective oxidation of polyunsaturated fatty acids by cytochrome P450BM-3

Deoxy-sugars often play a critical role in modulating the potency of many bioactive natural products. Accordingly, there has been sustained interest in methods for their synthesis over the past several decades. The focus of much of this work has been on developing new glycosylation reactions that permit the mild and selective construction of deoxyglycosides. This Review covers classical approaches to deoxyglycoside synthesis, as well as more recently developed chemistry that aims to control the selectivity of the reaction through rational design of the promoter. Where relevant, the application of this chemistry to natural product synthesis will also be described.

/pdf/methods-for-2-deoxyglycoside-synthesis-1kf8sby4iz.pdf

Methods for 2-Deoxyglycoside Synthesis.

Catalytic glycosylation has been a central reaction in carbohydrate chemistry since its introduction by Fischer 125 years ago, but it is only in the past three to four decades that catalytic methods for synthesizing oligosaccharides have appeared. Despite the development of numerous elegant and ingenious catalytic glycosylation methods, only a few are in general use. This review covers all methods of catalytic glycosylation with the focus on the development and application in oligosaccharide synthesis and provide an overview of the scope and limitations of these. The review also includes relevant mechanistic studies of catalytic glycosylations. The future of catalytic glycosylation chemistry is discussed, including specific, upcoming methods and possible directions for the field of research in general.

Catalytic Glycosylations in Oligosaccharide Synthesis

The synthesis of 2-deoxyglycosides : 1988-1999

An efficient catalytic procedure for the preparation of 2-deoxyglucosides from glucals without allylic or Ferrier rearrangement using triphenylphosphine hydrobromide and a wide variety of hydroxylic nucleophiles is described

Sang Gyeong Lee

Papers

Direct preparation of 2-deoxy-d-glucopyranosides from glucals without ferrier rearrangement

Direct Preparation of 2‐Deoxy‐D‐glucopyranosides from Glucals without Ferrier Rearrangement.

Enantiospecific synthesis of 17- and 18-hydroxyeicosatetraenoic acids, cytochrome P450 arachidonate metabolites

Synthesis of alcohols via mild oxidation of perfluoroethylstannanes

vic-Diol chirons: Enantiospecific synthesis of 11,12- and 14,15-dihydroxyeicosatrienoic acids