Sugar derivatives having sulfur in the ring

Fernandez‐Bolanos, J.; Al‐Masoudi, Najim A.; Maya, Inés

doi:10.1016/s0065-2318(01)57015-8

Cited by 34 publications

(10 citation statements)

References 369 publications

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“…[1] To date, except for 5-thio--mannose, which was isolated in 1987 from marine sponge Clathria pyramida, [2] thiosugars have not been found in nature. Since the first synthesis of a 5-thio--hexopyranose in 1961, [3] thiosugars have been obtained by the transformation of natural monosaccharides.…”

Section: Introductionmentioning

confidence: 99%

A Straightforward and General Strategy Towards 1,5‐Dithio‐1‐enopyranosides

2008

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Section: Introductionmentioning

confidence: 99%

A Straightforward and General Strategy Towards 1,5‐Dithio‐1‐enopyranosides

2008

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“…Although replacement of the sugar ring oxygen by sulfur provides close mimics of natural sugars, it is noteworthy, that the sulfur atom is larger and more polarizable than oxygen and the carbon-sulfur bond is longer (C-S, 0.182 nm vs. C-O, 0.143 nm), weaker and less polar than a carbon-oxygen bond (electronenegativities on the Sanders scale: O, 3.65; S, 2.96; C, 2.75). 27 Such differences are responsible for significant alterations in the anomeric effect, conformational behavior, chemical reactivity, molecular recognition by proteins, biological activity, 28 and metabolic stability of thiosugars analogues in comparison with their oxygen counterparts. For example, mutarotation of such thiosugars is reported to be base- but not acid-catalyzed resulting from the lower basicity of sulfur compared to oxygen in natural sugars.…”

Section: Introductionmentioning

confidence: 99%

S-Ribosylhomocysteine analogs containing a [4-thio]ribose ring

Sobczak

Chbib

Wnuk

2015

Carbohydrate Research

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The [4-thio]-S-ribosylhomocysteine (SRH) analogues containing substitution of a sulfur atom for the endocyclic oxygen were synthesized by coupling of the 4-thioribose substrates with a thiolate generated from the protected homocysteine. Coupling of the protected 1-deoxy-5-O-mesyl-S-oxo-4-thio-D-ribofuranose with homocysteinate salt gave the C4 epimers of [4-thio]-SRH at the sulfoxide oxidation level lacking a hydroxyl group at anomeric carbon. Treatment of these sulfoxides with BF3·Et2O/NaI effected simultaneous reduction to sulfide and global deprotection affording 1-deoxy-4-thio-SRH analogue. Treatment of the protected 1-deoxy-S-oxo-4-thio-D-ribofuranose sulfoxide with DAST/SbCl3 resulted in the fluoro-Pummerer rearrangement to give 4-thio-β-D-ribofuranosyl fluoride. Mesylation of the latter at 5-hydroxyl position followed by coupling with homocysteinate salt and subsequent global deprotection with trifluoroacetic acid afforded [4-thio]-SRH thiohemiacetal.

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“…As a consequence, 5-thio-galactose shows differences in the anomeric effect, conformational behavior and chemical reactivity. [11-13] Also, molecular interactions of 5-thio-galactose and of other 5-thio-pyranoses with enzymes may differ from those of pyranoses containing oxygen. Some 5-thio-pyranoses are glycosidase inhibitors [14,15] and in vitro studies have shown that bacterial and plant glycosidases do not hydrolyze the sulfur derivatives [16-18] or do so only at a very low rate.…”

Section: Introductionmentioning

confidence: 99%

Thiogalactopyranosides are Resistant to Hydrolysis by α‐Galactosidases

et al. 2012

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Fluorescently tagged glycosides containing terminal α(1→3) and α(1→4)-linked thio-galactopyranosides have been prepared and tested for resistance to hydrolysis by α-galactosidases. Eight fluorescent glycosides containing either galactose or 5-thio-galactose as the terminal sugar were enzymatically synthesized using galactosyltransferases with lactosyl glycosides as acceptors and UDP-galactose or UDP-5′-thio-galactose, respectively, as donors. The glycosides were incubated with human α-galactosidase A (CAZy family GH27, a retaining glycosidase), Bacteroides fragilis α-1,3-galactosidase (GH110, an inverting glycosidase) or homogenates of MCF-7 human breast cancer cells and NG108-15 rat glioma cells. Substrate hydrolysis was monitored by capillary electrophoresis with fluorescence detection. All compounds containing terminal O-galactose were readily degraded. Their 5-thio-galactose counterparts were resistant to hydrolysis by human α-galactosidase A and the enzymes present in the cell extracts. B. fragilis α-1,3-galactosidase hydrolyzed both thio- and O-galactoside substrates, however, the thio-galactosides were hydrolyzed at only 1-3% of the rate of O-galactosides. The hydrolytic resistance of 5-thio-galactose was also confirmed by an in vivo study using cells in culture. The results suggest that 5-thio-galactosides maybe useful tools for the study of anabolic pathways in cell extracts or in single cells.

show abstract

Sugar derivatives having sulfur in the ring

Cited by 34 publications

References 369 publications

A Straightforward and General Strategy Towards 1,5‐Dithio‐1‐enopyranosides

A Straightforward and General Strategy Towards 1,5‐Dithio‐1‐enopyranosides

S-Ribosylhomocysteine analogs containing a [4-thio]ribose ring

Thiogalactopyranosides are Resistant to Hydrolysis by α‐Galactosidases

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