Developments in the Chemistry of Thio Sugars

Horton, Derek; Hutson, D. H.

doi:10.1016/s0096-5332(08)60242-8

Cited by 79 publications

(28 citation statements)

References 301 publications

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“…[61] An alternative synthetic route involving S-glycosyl isothiouronium intermediates [62] was reinvestigated for the preparation of alkyl thioglycosides: The intermediates were prepared from the corresponding glycosyl bromides and thiourea, and then converted into thioglycosides by S-alkylation in the presence of a mild base and an appropriate alkyl halide. [63] Thioglycosides have also been prepared by the treatment of glycosyl bromides with nucleophilic thiolates generated in situ through the zincmediated reduction of disulfides.…”

Section: Thioglycosidesmentioning

confidence: 99%

New Principles for Glycoside‐Bond Formation

2009

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Increased understanding of the important roles that oligosaccharides and glycoconjugates play in biological processes has led to a demand for significant amounts of these materials for biological, medicinal, and pharmacological studies. Therefore, tremendous effort has been made to develop new procedures for the synthesis of glycosides, whereby the main focus is often the formation of the glycosidic bonds. Accordingly, quite a few review articles have been published over the past few years on glycoside synthesis; however, most are confined to either a specific type of glycoside or a specific strategy for glycoside synthesis. In this Review, new principles for the formation of glycoside bonds are discussed. Developments, mainly in the last ten years, that have led to significant advances in oligosaccharide and glycoconjugate synthesis have been compiled and are evaluated.

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Section: Thioglycosidesmentioning

confidence: 99%

New Principles for Glycoside‐Bond Formation

2009

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“…From the synthetic point of view, the importance of 1-thioaldoses and 1-thioglycosides has been recognized for a long time, and 1- S -alkylation routes to thioglycosides, which are easier to perform than the corresponding 1- O -alkylation methods, were documented by Horton already in the early 1960s [17]. Recently, these molecules are gaining renewed interest, and have found numerous novel applications in, for example, biohybrid polymer systems [18–20], dynamic combinatorial chemistry (DCC) [21–24], glycoclusters based on self-organizable scaffolds [25–27], glycoporphyrin-assisted photodynamic therapy (PDT) [25,28,29], bio-nanotechnology [30–32], and biologically important glycoconjugates [15,33].…”

Section: Introductionmentioning

confidence: 99%

Stereocontrolled 1-S-glycosylation and comparative binding studies of photoprobe-thiosaccharide conjugates with their O-linked analogs

Deng

Wang

Uppalapati

et al. 2013

Pure and Applied Chemistry

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The use of thioglycosides and other glycan derivatives with anomeric sulfur linkages is gaining increasing interest, both in synthesis and in various biological contexts. Herein, we demonstrate the occurrence and circumvention of anomerization during 1-S-glycosylation reactions, and present highly efficient and stereocontrolled syntheses of a series of photoprobe-thiosaccharide conjugates. Mutarotation of glycosyl thiols proved to be the origin of the anomeric mixtures formed, and kinetic effects could be used to circumvent anomerization. The synthesized carbohydrate conjugates were then evaluated by both solution- and solid-phase-based techniques. Both binding results showed that the S-linked glyco-sides interact with their cognate lectins comparably to the corresponding O-analogs in the present cases, thus demonstrating the reliability of the solid-support platform built upon our photo-initiated carbohydrate immobilization method for probing protein bindings, and showing the potential of combining these two means for studying carbohydrate–protein interactions.

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“…It was early recognized that mercury had a high affinity for the sulfur functionality [4], and effective hydrolysis of 1 -thiofuranosides using mercuric chloride as catalyst instead of a mineral acid was reported [70]. An early attempt to methanolyze ethyl tetra-0-acetyl-1 -thio-P-D-mannopyranoside using HgC12 was nct successful [71], but when Ferrier et al tried alcoholysis on unprotected phenyl 1 -thio-D-glucopyranosides using Hg(0Ac)z or HgClz/HgO as promoters good yields of the corresponding alkyl glycosides with inverted anomeric configuration was obtained [8, 721.…”

Section: Heavy Metal Salt Promotorsmentioning

confidence: 99%

Thioglycosides

Ernst

Hart

Sînaÿ

2000

Carbohydrates in Chemistry and Biology

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Thioglycosides are not very common in nature, only a few simple alkyl and aryl thioglycosides have been found as constituents of antibiotics from Streptomyces species [ 1-31. Although not really thioglycosides, glucosinolates with an anomeric sulfur are also well-known natural compounds [4, 51. In spite of their low natural abundance, thioglycosides and their chemistry have for a long time been a field of interest for many researchers, the first thioglycoside was synthesized in 1909 [6], and their basic chemistry was early reviewed [4, 71. But it is only recently that their excellent glycosyl donor qualities have been recognized. In the beginning of the seventies the first successful synthesis of a disaccharide was performed [S], but it was not until the middle of the eighties that enough efficient promoters were discovered to make glycosylation with thioglycoside donors into a general and accepted method. Since then and in a very short time-span, thioglycosides have become one of the most used type of donors, especially in glycosylations with oligosaccharide donors (block synthesis). There are already some reviews on the subject [9-121, and in the most recent complete list of published glycosylations during one year (1994) [ 131, thioglycosides were used as donors in about 20% of all reported glycosylations and in 35% of all couplings using oligosaccharide donors, competing well with the long established halide donors and the trichloroacetimidate method.The strength of thioglycosides as glycosyl donors is their easy synthesis (Section 4.2) combined with their stability, withstanding most reaction conditions used in e.g. protecting group manipulations and glycosylations, and at the same time their effective acth ation using chemoselective thiophilic promoters (Sections 4.3.2 and 4.4.1) and also easy transformation into other types of glycosyl donors (Section 4.3.1). Hence, they are perfectly fitted to be used in block synthesis of oligosaccharides, where stable oligosaccharide donors are a prerequisite. Their stability also makes them very apt in synthetic schemes where a number of chemical modifications are performed just prior to the glycosylations, as, e.g., in various types of Carbohydrates in Chemistry and Biology

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Developments in the Chemistry of Thio Sugars

Cited by 79 publications

References 301 publications

New Principles for Glycoside‐Bond Formation

New Principles for Glycoside‐Bond Formation

Stereocontrolled 1-S-glycosylation and comparative binding studies of photoprobe-thiosaccharide conjugates with their O-linked analogs

Thioglycosides

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