Archives for Chemistry Experiments of 2,3,4,6-Tetra-o-acetyl-D-glucopyranose

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N-aryl-O-glycosyl haloacetimidates as glycosyl donors

Reaction of 1-O-unprotected tetra-O-acetyl- and tetra-O-benzyl- glucopyranose with N-aryl haloacetimidoyl chlorides in the presence of sodium hydride and 15-crown-5 afforded N-aryl-O-glucopyranosyl haloacetimidates. Mainly the beta-anomers were obtained in this anomeric O-acylation-type reaction. The glycosyl donor properties of these haloacetimidates were investigated with 6-O- and 4-O-unprotected glucopyranosides as acceptors. The results were compared with those obtained with the corresponding O-glucopyranosyl trichloroacetimidates as glycosyl donors and the same acceptors. It was found that N-(2-chloro-6-methylphenyl)-O-glucopyranosyl trifluoroacetimidates (16Ad, 16Bd) exhibit glycosyl donor properties closely related to those of the corresponding N-unsubstituted O-glucopyranosyl trichloroacetimidates (12A, 12B). Copyright Taylor & Francis Group, LLC.

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Enzyme-labile protecting groups in peptide synthesis: Development of glucose- and galactose-derived urethanes

The development of the tetra-O-acetyl-D-glucopyranosyloxycarbonyl (AGlOC) and tetra-O-acetyl-beta-D-galactopyranosyloxycarbonyl (AGalOC) protecting groups, which are fully enzyme-labile, carbohydrate-derived urethanes, is described. The protected amino acids were easily synthesized and subsequently converted into a series of model dipeptides through classical peptide couplings. Cleavage of an alpha/beta-anomeric mixture of a model AGlOC dipeptide was achieved with a ‘one-pot’ procedure in good yield. To gain a better understanding of the enzymatic deprotection reaction, the AGalOC group was removed formation (lipase catalyzed deacetylation, followed by beta-galactosidase catalyzed glycosidic bond fragmentation). Under these very mild reaction conditions (aq. buffer pH7.0, 37C), the desired N-terminal, unprotected dipeptide conjugates were obtained. The methodology was further utilized for the synthesis of an advanced tetrapeptide model system.

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The total syntheses of D-erythro-sphingosine, N-palmitoylsphingosine (ceramide), and glucosylceramide (cerebroside) via an azidosphingosine analog

The total synthesis of D-erythro-sphingosine (9) was performed by a chirospecific method starting from D-galactose via an azidosphingosine intermediate to give highly homogeneous ( > 99.9% C18:1) sphingosine base (9) which contained no observable olefin isomerization by product and was demonstrated to be optically pure by a novel method utilizing Mosher’s acid. Ceramide (10) was prepared from this sphingosine (9) with highly homogeneous (99.8% C16:0) palmitic acid by two methods. The cerebroside glucosylceramide (23) was the next sphingolipid in this series to be synthesized in a highly homogeneous form. These three sphingolipids are currently being used for biophysical studies of the structures of their hydrated bio-molecular assemblies.

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Tetrahydropyran – Wikipedia,
Tetrahydropyran – an overview | ScienceDirect Topics

Discovery of 2,3,4,6-Tetra-o-acetyl-D-glucopyranose

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Synthesis of 1,3-di-O-alkyl-2-O-(beta-glycosyl)glycerols bearing oligosaccharides as hydrophilic groups

A novel series of synthetic glycolipids, 1,3-di-O-alkyl-2-O-(beta-glycosyl)glycerols, and their efficient synthetic route were proposed.These glyceroglycolipids were synthesized in good overall yields and stereoselectivity in five steps via trichloroacetimidate glycosylation with 1,3-di-O-alkylglycerols.This route was applied to prepare the glycolipids bearing a cello- or malto-oligosaccharide with a definite number of sugar residues from one to six.Thin-layer chromatography, elemental analysis, nuclear magnetic resonance spectroscopy and infrared absorption spectroscopy confirmed that these glycolipids were chemically pure compounds.Keywords: Glyceroglycolipids; Oligosaccharide headgroups; Synthesis

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Synthesis of 3,3?-neotrehalosadiamine and related 1,1?-aminodisaccharides using disarmed, armed, and superarmed building blocks

Here we report a high yielding, stereoselective synthesis of the naturally occurring 1,1?-disaccharide neotrehalosadiamine (NTD) and some related analogs. Following an eleven-step sequence, seven of which did not require chromatographic separation, NTD was generated in 60% overall yield from the inexpensive, commercially available precursor 1,2:5,6-di-O-isopropylidene- alpha-delta-glucofuranose. The key a,b-linkage of NTD was formed in a highly stereoselective manner by taking advantage of the participating effect of the acyl group at O-2 of the donor glycoside. The influence of electronic effects of disarmed, armed, and superarmed glycosyl donors and acceptors on the outcome of 1,1?-glycosidation was also observed. Antibacterial studies using NTD and its analogs show detectable but weak antistaphylococcal activity.

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Tetrahydropyran – Wikipedia,
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First O-glycosylation of hydroxamic acids

(Chemical Equation Presented) The first O-glycosylation of hydroxamic acids is reported. This process involves the use of glycosyl N-phenyl trifluoroacetimidates as glycosyl donors in the presence TMSOTf and 4 A molecular sieves in dichloromethane. Under such conditions, a wide range of new glycosyl donors including glucosyl, galactosyl, mannosyl, glucuronyl, and ribosyl hydroxamates were prepared in good to high yields. This procedure appears to be an advantageous alternative for the synthesis of glycosyl hydroxamates of biological interest.

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Selective photoregulation of the activity of glycogen synthase and glycogen phosphorylase, two key enzymes in glycogen metabolism

Glycogen is a polymer of alpha-1,4- and alpha-1,6-linked glucose units that provides a readily available source of energy in living organisms. Glycogen synthase (GS) and glycogen phosphorylase (GP) are the two enzymes that control, respectively, the synthesis and degradation of this polysaccharide and constitute adequate pharmacological targets to modulate cellular glycogen levels, by means of inhibition of their catalytic activity. Here we report on the synthesis and biological evaluation of a selective inhibitor that consists of an azobenzene moiety glycosidically linked to the anomeric carbon of a glucose molecule. In the ground state, the more stable (E)-isomer of the azobenzene glucoside had a slight inhibitory effect on rat muscle GP (RMGP, IC50 = 4.9 mM) and Escherichia coli GS (EcGS, IC50 = 1.6 mM). After irradiation and subsequent conversion to the (Z)-form, the inhibitory potency of the azobenzene glucoside did not significantly change for RMGP (IC50 = 2.4 mM), while its effect on EcGS increased 50-fold (IC50 = 32 muM). Sucrose synthase 4 from potatoes, a glycosyltransferase that does not operate on glycogen, was only slightly inhibited by the (E)-isomer (IC50 = 0.73 mM). These findings could be rationalized on the basis of kinetic and computer-aided docking analysis, which indicated that both isomers of the azobenzene glucoside mimic the EcGS acceptor substrate and exert their inhibitory effect by binding to the glycogen subsite in the active center of the enzyme. The ability to selectively photoregulate the catalytic activity of key enzymes of glycogen metabolism may represent a new approach for the treatment of glycogen metabolism disorders.

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Hydrogen phosphorous acid monoester intermediates synthetic sugar-1-mono phosphoric acid method (by machine translation)

The invention belongs to the field of chemical synthesis and relates to synthesis of glycosyl-1-monophosphate. The method disclosed by the invention comprises the following steps of 1, performing a reaction between imidazole and phosphorus trichloride to obtain phosphite tri-imidazole, performing a reaction between the phosphite tri-imidazole and an acetylated sugar raw material of which the end position is deprotected and carrying out in-situ hydrolysis to obtain corresponding glycosyl-1-hydrogen phosphite monoester; 2, carrying out silylation on the glycosyl-1-hydrogen phosphite monoester by N,O-bi(trimethylsilyl)acetamide to obtain a trialkylphosphite intermediate, carrying out oxidation on an organic alkali/iodine simple substance system and carrying out in-situ hydrolysis to obtain glycosyl-1-monophosphate protected by acetyl; 3, removing an acetyl protecting group through sodium methylate and obtaining corresponding the high-purity glycosyl-1-monophosphate through sephadex chromatographic purification and ion exchange. According to the method disclosed by the invention, the glycosyl-1-monophosphate is obtained through the three steps and the total yield can reach 75 percent to 85 percent. Loss caused by benzyl removing by hydrogenation in a conventional method is avoided. The method disclosed by the invention is particularly suitable for preparing a great amount of glycosyl-1-monophosphate.

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A new glycosidation method through nitrite displacement on substituted nitrobenzenes

Benzyl, benzoyl, and acetyl protected 1-OH and 1-SH glycoses in the glucose, glucosamine, galactose, mannose, and lactose series react with nitrobenzenes activated by one or two electron withdrawing substituents like nitro and cyano to afford the corresponding aryl glycosides in 50-100% yield. The SNAr displacement of nitrite by 1-OH glycoses is reversible and gives predominantly the alpha-glycosides, whereas 1-SH glycoses do not anomerize and afford the beta-glycosides. Thus, the prepared dicyanophenyl gycosides are useful building blocks for the preparation of phthalocyanine-glycoconjugates via template synthesis.

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A Dinuclear Dysprosium Complex as an Air-Stable and Recyclable Catalyst: Applications in the Deacetylation of Carbohydrate, Aliphatic, and Aromatic Molecules

Two dinuclear DyIII complexes, [Dy2(hmb)2(OTf)2(H2O)4]?HOTf?2 THF (A?HOTf?2 THF) and [Dy2(hmi)3(H2O)2]?2 HOTf (B?2 HOTf), have been synthesized by the reaction of Dy(OTf)3 and the Schiff-base ligands H2hmb (N?-(2-hydroxy-3-methoxybenzylidene)benzohydrazide) or H2hmi ((2-hydroxy-3-methoxyphenyl)methylene isonicotinohydrazine). Disarmed glycosyl trichloroacetimidates can be activated by complex A in the synthesis of 1,2-trans-glycosides with primary and secondary acceptors. This method offers an efficient route to selectively deacetylated monosaccharides and disaccharides in high yields and a green catalyst that can be easily recycled and reused.

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