Discovery of N-((2S,3R,4R,5R,6R)-2,4,5-Trihydroxy-6-(hydroxymethyl)tetrahydro-2H-pyran-3-yl)acetamide

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Three sugar 1-phosphates that are donor substrates for phosphorylases were produced at the gram scale from phosphoenolpyruvic acid and the corresponding sugars by the combined action of pyruvate kinase and the corresponding anomeric kinases in good yields. These sugar 1-phosphates were purified through two electrodialysis steps. alpha-d-Galactose 1-phosphate was finally isolated as crystals of dipotassium salts. alpha-d-Mannose 1-phosphate and 2-acetamido-2-deoxy-alpha-d-glucose 1-phosphate were isolated as crystals of bis(cyclohexylammonium) salts.

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Tetrahydropyran – Wikipedia,
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The present invention relates to a process for the synthesis of L-fucosyl di- or oligosaccharides and their novel 2,3,4-tri-O-benzyl-fucosyl synthetic intermediates derivatives of easy crystallization. In particular the present invention relates to a process applicable to industrial scale for the synthesis of 2?O-fucosyl lactose.

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Reference:
Tetrahydropyran – Wikipedia,
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The invention discloses a method used for catalytic reduction of imine with saccharide-derivatized amino alcohol. According to the method, imine is taken as a substrate. The method comprises following steps: 1) imine and saccharide-derivatized amino alcohol are dissolved in an organic solvent I, wherein molar ratio of imine to saccharide-derivatized amino alcohol ranges from 100:1-20; 2) trichlorosilane with 1.5 to 5 times equivalent weights is added into a solution obtained via step 1) dropwise, an obtained mixture is stirred and reacted for 12 to 36h at a temperature of -20 to 40 DEG C, and a saturated sodium bicarbonate solution is used for quenching; 3) a material obtained via step 2) is extracted with an organic solvent II, and is subjected to column chromatography isolation so as to obtain amine compounds.

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Tetrahydropyran – Wikipedia,
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Members of a family of functionally and stereochemically diverse d-glucosamine-derived tertiary aminoalcohol ligands have been used to promote the asymmetric Reformatsky reaction. The beta-hydroxyester product tert-butyl 3-phenyl-3-hydroxy-propanoate was obtained enriched in either the (+)-(R) (up to 74% ee) or (-)-(S) (up to 42% ee) enantiomer depending on the choice of ligand. Although the selectivities are modest in absolute terms they represent some the better selectivities obtained to date for this reaction. A 1H NMR study was conducted to investigate this selectivity and suggested a secondary binding mode between ligand and zinc in addition to the expected N-2, O-3 coordination.

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Reference:
Tetrahydropyran – Wikipedia,
Tetrahydropyran – an overview | ScienceDirect Topics

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The syntheses of four analogues of N4-(2-acetamido-2-deoxy-beta-D-glucopyranosyl)-L-asparagine are described. Activated carboxylic acids were reacted with 2-acetamido-2-deoxy-beta-D-glucopyranosylamine. n-Butyric anhydride gave N-(2-acetamido-2-deoxy-beta-D-glucopyranosyl)-n-butyramide. 3-Chloropropionic anhydride was synthesized from 3-chloropropionic acid and gave N-(2-acetamido-2-deoxy-beta-D-glucopyranosyl)-3-chloropropionamide. Equilibration of the latter with ammonium bicarbonate gave N1-(2-acetamido-2-deoxy-beta-D-glucopyranosyl)-3- aminopropionamide. Succinimidyl isovalerate was synthesized and gave N-(2-acetamido-2-deoxy-beta-D-glucopyranosyl)isovaleramide.

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Tetrahydropyran – Wikipedia,
Tetrahydropyran – an overview | ScienceDirect Topics

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Indium(III) trifluoromethanesulfonate has been found to be extremely efficient in catalyzing acyl transfer reactions of various carbohydrates and their derivatives. Selective acetolyses of certain benzyl ethers/isopropylidene acetals of sugars have been possible using In(OTf)3 in Ac2O (neat). Reaction of the per-O-acetate of 2-deoxy-2-phthalimido-D-glucose with benzyl mercaptan in the presence of In(OTf)3 led to the formation of the corresponding thioglycoside in high yield. Facile formation and hydrolysis of the isopropylidene and benzylidene acetals of various carbohydrates have also been achieved very efficiently in the presence of In(OTf)3. The results show great promise for In(OTf)3 in synthetic carbohydrate chemistry.

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Reference:
Tetrahydropyran – Wikipedia,
Tetrahydropyran – an overview | ScienceDirect Topics

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Expansion of the genetic code with unnatural amino acids (Uaas) has significantly increased the chemical space available to proteins for exploitation. Due to the inherent limitation of translational machinery and the required compatibility with biological settings, function groups introduced via Uaas to date are restricted to chemically inert, bioorthogonal, or latent bioreactive groups. To break this barrier, here we report a new strategy enabling the specific incorporation of biochemically reactive amino acids into proteins. A latent bioreactive amino acid is genetically encoded at a position proximal to the target natural amino acid; they react via proximity-enabled reactivity, selectively converting the latter into a reactive residue in situ. Using this Genetically Encoded Chemical COnversion (GECCO) strategy and harnessing the sulfur-fluoride exchange (SuFEx) reaction between fluorosulfate-l-tyrosine and serine or threonine, we site-specifically generated the reactive dehydroalanine and dehydrobutyrine into proteins. GECCO works both inter- and intramolecularly, and is compatible with various proteins. We further labeled the resultant dehydroalanine-containing protein with thiol-saccharide to generate glycoprotein mimetics. GECCO represents a new solution for selectively introducing biochemically reactive amino acids into proteins and is expected to open new avenues for exploiting chemistry in live systems for biological research and engineering.

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Tetrahydropyran – Wikipedia,
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The binding properties of the rat sublingual glycoprotein (RSL) and its asialo product with lectins were characterized by quantitative precipitin (QPA) and precipitin inhibition (QPIA) assays. Among twenty lectins tested for QPA, native RSL reacted well only with Artocarpus integrifolia (jacalin) but weakly or not at all with the other lectins. However, its asialo product (asialo-RSL) reacted strongly with many Gal and GalNAc specific lectins- it bound best to three of the GalNAcalpha1?Ser/Thr (II) and/or Galbeta1?4GlcNAc active lectins [jacalin, Wistaria floribunda and Ricinus communis agglutinins] and completely precipitated each of these three lectins. Asialo-RSL also reacted well with Abrus precatorius, Glycine max Bauhinia purpurea alba, and Maclura pomifera agglutinins and abrin-a, but not with Arachis hypogeae and Dolichos biflorus agglutinins. The interaction between asialo-RSL and lectins were inhibited by either Galbeta1?4GlcNAc, p-NO2-phenylalpha-GalNAc or both. The mapping of the precipitation and inhibition profiles leads to the conclusion that the asialo rat sublingual glycoprotein provides important ligands for II(Galbeta1?4GlcNAcbeta1?) and Tn(GalNAcalpha1 ?Ser/Thr) active lectins.

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Tetrahydropyran – Wikipedia,
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Palladium-catalyzed oxidation of isopropyl N-acetyl-alpha-d-glucosamine (GlcNAc) is used to prepare the rare sugars allosamine, lividosamine, and related compounds with unprecedented selectivity. The Passerini reaction applied on 3-keto-GlcNAc provides an entry into branching of the carbon skeleton in this compound.

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Reference:
Tetrahydropyran – Wikipedia,
Tetrahydropyran – an overview | ScienceDirect Topics

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2,2-Bipyridines having beta-lactoside, beta-d-glucoside, beta-d-galactoside, and N-acetyl-beta-d-glucosaminide were prepared and then, complexed with ferrous ion to afford trivalent glycoclusters having tris-bipyridine ferrous complex cores. Each glycocluster provides a dynamic combinatorial library composed of four diastereomeric stereoisomers (Deltamer, Deltafac, Lambdamer, and Lambdafac) whose ratios depend on their relative stabilities. CD spectral analyses of these glycoclusters showed that various cations (Na+, Mg2+, K+ or Ca2+) enriched Delta-forms of the glycocluster having beta-lactosides and N-acetyl-beta-d-glucosaminides possibly by cations-induced intramolecular carbohydrate-carbohydrate interactions.

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Reference:
Tetrahydropyran – Wikipedia,
Tetrahydropyran – an overview | ScienceDirect Topics