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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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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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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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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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Tetrahydropyran – Wikipedia,
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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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Tetrahydropyran – Wikipedia,
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In the nematode model organisms Caenorhabditis elegans and Pristionchus pacificus, a new class of natural products based on modular assembly of primary-metabolism-derived building blocks control organismal development and behavior. We report identification and biological activities of the first pentamodular metabolite, pasa#9, and the 8-oxoadenine-containing npar#3 from P. pacificus. These structures suggest co-option of nucleoside and tryptophan metabolic pathways for the biosynthesis of endogenous metabolite libraries that transcend the dichotomy between primary and secondary metabolism.

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(Chemical Equation Presented) Chitin synthase (CS) polymerizes UDP-GlcNAc to form chitin (poly-beta(1,4)-GlcNAc), a key component of fungal cell wall biosynthesis. Little is known about the substrate specificity of chitin synthase or the scope of substrate modification the enzyme will tolerate. Following a previous report suggesting that 6-O-dansyl GlcNAc is biosynthetically incorporated into chitin, we became interested in developing an assay for CS activity based on incorporation of a fluorescent substrate. We describe the synthesis of two fluorescent UDP-GlcNAc analogues and their evaluation as chitin synthase substrates.

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Tetrahydropyran – Wikipedia,
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Green glycosylation of functionalized alcohols and alpha-amino acids, using an ionic liquid as a recyclable solvent, was performed in one step directly from the unprotected monosaccharide under scandium triflate or ferric chloride catalysis. Pure alpha- and beta-glycosides could be obtained after specific enzymatic hydrolysis.

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An efficient streamlined chemoenzymatic approach has been developed for gram-scale synthesis of Lewis a angtigen (LeabetaProN3) and a library of sialyl Lewis a antigens (sLeabetaProN3) containing different sialic acid forms. Intially, commercially available inexpensive N-acetylglucosamine (GlcNAc) was converted to its N?-glycosyl p-toluenesulfonohydrazide in one step. Followed by chemical glycosylation, GlcNAcbetaProN3 was synthesized using this protecting group-free method in high yield (82%). Sequential one-pot multienzyme (OPME) beta1?3-galactosylation of GlcNAcbetaProN3 followed by OPME alpha1?4-fucosylation reactions produced target LeabetaProN3 in gram-scale. Structurally diverse sialic acid forms was successfully introduced using a OPME sialylation reation containing a CMP-sialic acid synthetase and Pasteurella multocida alpha2?3-sialyltransferase 1 (PmST1) mutant PmST1 M144D with or without a sialic acid aldolase to form sLeabetaProN3 containing naturally occurring or non-natural sialic acid forms in preparative scales.

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Tetrahydropyran – Wikipedia,
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The bromotropolones (4), (5) and (10) undergo palladium-mediated cross coupling with a wide range of organostannanes to produce alkenyl-, alkyl- and aryl-substituted tropolones.The methodology has been applied to the synthesis of the monoterpenes beta-dolabrin (11), beta-thujaplicin (12), 4-isopropyl-7-methoxytropolone (13) and beta-thujaplicinol (14).Cross coupling of bromotropolones (4), (5) and (10) with various aryltrimethylstannanes or arylboronic acids has permitted the preparation of the bicyclic colchicine analogues (30)-(43) which have been tested for tubulin-binding activity.The X-ray crystal structure of the most active of these systems, compound (38), is reported.

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Tetrahydropyran – Wikipedia,
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