A General Procedure for Conversion of S-Glycosyl Isothiourea Derivatives into Thioglycosides, Thiooligosaccharides and Glycosyl Thioesters

Ibatullin, Farid M.; Селиванов, С. И.; Шавва, А. Г.

doi:10.1055/s-2001-11443

Cited by 53 publications

(28 citation statements)

References 9 publications

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“…Recently, Ibatullin and coworkers [24,25] described a facile procedure for the conversion of isothiouronium salts of sugars into thioglycosides, thiooligosaccharides, and glycosylthioesters. For the synthesis of thiodisaccharides or thiooligosaccharides, [25] the triethylamine-promoted reaction of the glycosyl isothiouronium bromide with a conveniently protected triflate derivative of a sugar was employed.…”

Section: Resultsmentioning

confidence: 99%

Stereoselective Synthesis of 3‐Deoxy‐4‐S‐(1→4)‐Thiodisaccharides and Their Inhibitory Activities Towards β‐Glycoside Hydrolases

2005

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The sulfur linkage of β‐(1→4)‐thiodisaccharides was constructed with excellent diastereoselectivity by Michael addition of 2,3,4,6‐tetra‐O‐acetyl‐1‐thio‐β‐D‐galactose (2) or its β‐D‐glucose isomer (3) to sugar‐derived (2S, 6S)‐6‐acetoxymethyl‐2‐(2‐propyloxy)‐2H‐pyran‐3(6H)‐one (1). These reactions led to the per‐O‐acetyl glycosides of 3‐deoxy‐4‐S‐glycopyranosyl‐4‐thiohexopyranosid‐2‐ulose (4 and 5, respectively). Similar conjugated addition to the enone 1 of the isothiouronium salts 6 or 7, precursors in the synthesis of 2 or 3, also afforded the thiodisaccharides 4 or 5, respectively, with exclusive formation of the isomer that has an R configuration for the C‐4 stereocenter of the reducing‐end. The carbonyl function of 4 and 5 was reduced, and the resulting products were O‐deacetylated to give the free 4‐S(1→4)‐thiodisaccharides 10, 11, 14, and 15, which have a deoxy functionality adjacent to the thio group. These compounds were tested as inhibitors of glycoside hydrolases. Thus 11, the 3‐deoxy‐4‐thiomimetic of Galβ(1→4)Gal, proved to be a competitive inhibitor of the β‐galactosidase from E. coli (Ki = 0.16 mM). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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Section: Resultsmentioning

confidence: 99%

Stereoselective Synthesis of 3‐Deoxy‐4‐S‐(1→4)‐Thiodisaccharides and Their Inhibitory Activities Towards β‐Glycoside Hydrolases

2005

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“…Ibatullin et al [32,33] described a one-pot procedure for the synthesis of thioglycosides and thioologosaccharides that employs directly the isothiouronium salts without isolation of the 1-thioaldose. The S-glycosylisothiouronium salts were prepared by reaction of thiourea with glycosyl halides [25], and the S-alkylation was promoted with triethylamine.…”

Section: I) Nucleophilic Displacement Of a Good Leaving Group In A Camentioning

confidence: 99%

“…The reaction conditions allowed the synthesis of glycosyl thioesters and some thioglycosides that could not be prepared using the traditional approach. The procedure was successfully applied for the synthesis of methyl 4-thio-α-cellobioside and methyl 4-thio-α-lactoside derivatives [32], and also for the preparation of thiooligosaccharides [33]. For example, the 4-thioxylotriose (65, n=1) was obtained by means of the triethylamine-promoted reaction of the glycosyl isothiouronium bromide 63 (n=1) with the triflate 64 (Scheme 13).…”

Section: I) Nucleophilic Displacement Of a Good Leaving Group In A Camentioning

confidence: 99%

Non-conventional Glycosidic Linkages: Syntheses and Structures of Thiooligosaccharides and Carbohydrates with Three-bond Glycosidic Connections

Varela¹

2006

COC

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Thiooligosaccharides display inhibitory activity against glycoside hydrolases and they constitute a valuable tool for structural biology. The construction of the interglycosidic linkage, in which the oxygen atom is replaced by sulfur, usually involves one of the following reactions: i) nucleophilic displacement of good leaving groups in a carbohydrate moiety by a sugar thiol, ii) Michael and Michael-type additions of sugar thiols to unsaturated acceptors, iii) ring-opening of aziridines and oxiranes by thiosugars, iv) enzyme-catalyzed couplings of thiosugar moieties. The application of these reactions for the syntheses of thiooligosaccharides are surveyed, and the biological activities of the resulting products briefly described. Carbohydrate structures incorporating three-bond glycosidic linkages with two heteroatoms are uncommon in Nature. The -N-O-interglycosidic bond in the oligosaccharide part of enediyne antibiotics is partly responsible for their potent antitumor activities. The disulfide bond which plays an essential role in proteins has recently been introduced as an interglycosidic connecting motif. The sulfenamide functionality is the sulfur analog of the hydroxylamine type glycosidic linkages in calicheamicins. Novel glycosylation strategies have recently been developed by taking advantage of unconventional, three-bond glycosidic linkages to construct neoglycoproteins and other glycoconjugates which are increasingly important tools in glycobiology and drug discovery. To explore conformational preferences and molecular flexibility in these structures NMR spectroscopy, chiroptical methods and X-ray crystallography are being used, supplemented by molecular modelling calculations. The structural features will be briefly discussed with relevance to biological interactions such as enzyme binding.

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“…[33] After some experimentation, the use of thiourea, as used for the preparation of thioglycosides, proved successful. [51][52][53] Compound 11 was treated with BF 3 ·Et 2 O and two equivalents thiourea. Subsequent addition of 12, together with an excess of base, resulted in the formation of 13 as the main product.…”

Section: Synthesis Of the Amide-and Triazole-linked Probesmentioning

confidence: 99%

Synthesis and Evaluation of New Thiodigalactoside‐Based Chemical Probes to Label Galectin‐3

et al. 2009

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New chemical probes were synthesized to label galectin-3. They are based on the high affinity thiodigalactoside ligand. The probes were synthesized with benzophenone or acetophenone moieties as the photolabel for covalent attachment to the protein. Besides labeling the protein, these aromatic photolabels also greatly enhance the affinity of the probes towards galectin-3, due to the interaction of the photolabel with two arginine guanidinium groups of the protein. The linkage between the sugar and the photolabel was varied as an ester, an amide, and a triazole. For the amide and triazole derivatives, a versatile synthetic route towards a symmetrical 3-azido-3-deoxy-thiodigalactoside was developed. The new probes were evaluated for their binding affinity of human galectin-3. They were subsequently tested for their labeling efficiency, as well as specificity in the presence of a protein mixture and a human cancer cell lysate.

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A General Procedure for Conversion of S-Glycosyl Isothiourea Derivatives into Thioglycosides, Thiooligosaccharides and Glycosyl Thioesters

Cited by 53 publications

References 9 publications

Stereoselective Synthesis of 3‐Deoxy‐4‐S‐(1→4)‐Thiodisaccharides and Their Inhibitory Activities Towards β‐Glycoside Hydrolases

Stereoselective Synthesis of 3‐Deoxy‐4‐S‐(1→4)‐Thiodisaccharides and Their Inhibitory Activities Towards β‐Glycoside Hydrolases

Non-conventional Glycosidic Linkages: Syntheses and Structures of Thiooligosaccharides and Carbohydrates with Three-bond Glycosidic Connections

Synthesis and Evaluation of New Thiodigalactoside‐Based Chemical Probes to Label Galectin‐3

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