- Glycopolymers via catalytic chain transfer polymerisation (CCTP), Huisgens cycloaddition and thiol-ene double click reactions
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CCTP has been used to give alkyne-functional macromonomers which are subsequently functionalised with sugar azides and thiols, using both CuAAC and thiol-ene Michael addition reactions, to yield end-functionalised glycopolymers in a convenient manner. The
- Nurmi, Leena,Lindqvist, Josefina,Randev, Rajan,Syrett, Jay,Haddleton, David M.
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Read Online
- Synthesis of a cellobiosylated dimer and trimer and of cellobiose-coated polyamidoamine (PAMAM) dendrimers to study accessibility of an enzyme, cellodextrin phosphorylase
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To examine the accessibility of the enzyme cellodextrin phosphorylase (CDP) towards multivalent cluster carbohydrates, the cellobiosylated dimer 10 and trimer 12, as well as the cellobiose-coated PAMAM dendrimers 14, 16, 18, 20 and 22, with four, eight, sixteen, thirty-two and sixty-four cellobiose units at the outer surface of PAMAM dendrimers, respectively, have been synthesized for the first time and used as acceptor substrates for the enzyme CDP. It was found that CDP was able to transfer a glucosyl moiety from glucose-1-phosphate (Glc-1-P) into these synthesized cluster cellobiosylated glycoconjugates and cellobiose-coated PAMAM dendrimers, which were thus acceptor substrates for CDP. It was found that the ability of CDP to interact with smaller cellobiosylated glyconjugates and with PAMAM dendrimers containing up to eight cellobiose units was similar to that seen with cellobiose. However, this capability of CDP was somewhat lessened with the PAMAM dendrimer containing sixteen cellobiose moieties and dramatically decreased towards PAMAM dendrimers with thirty-two and sixty-four cellobiose units. This might be due to their steric bulk, CDP enzyme no longer being able to hold them properly on its active site. ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).
- Choudhury, Ambar K.,Kitaoka, Mitomitsu,Hayashi, Kiyoshi
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Read Online
- Convenient synthesis of long alkyl-chain triazolylglycosides using ionic liquid as dual promoter-solvent: Readily access to non-ionic triazolylglycoside surfactants for evaluation of cytotoxic activity
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A convenient method for the one-pot synthesis of long alkyl-chain triazolylglycosides using ionic liquid as dual promoter and solvent is described via a sequential one-pot two-step glycosidation-CuAAc click reaction. The reaction was carried out using commercially available substrates, including glycosyl bromides, sodium azide and various long alkyl-chain alkynes to achieve the corresponding products in moderate to high yields. Furthermore, this approach was successfully applied for the preparation of non-ionic monocatenary triazolylglycoside surfactants in excellent yields through simple deacetylation. Subsequently, these surfactants were further evaluated for their cytotoxic activity.
- Ketsomboon, Nutthanicha,Saeeng, Rungnapha,Srisook, Klaokwan,Sirion, Uthaiwan
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- Design, synthesis of oleanolic acid-saccharide conjugates using click chemistry methodology and study of their anti-influenza activity
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The development of entry inhibitors is an emerging approach to the inhibition of influenza virus. In our previous research, oleanolic acid (OA) was discovered as a mild influenza hemagglutinin (HA) inhibitor. Herein, as a further study, we report the preparation of a series of OA-saccharide conjugates via the CuAAC reaction, and the anti-influenza activity of these compounds was evaluated in vitro. Among them, compound 11b, an OA-glucose conjugate, showed a significantly increased anti-influenza activity with an IC50 of 5.47 μM, and no obvious cytotoxic effect on MDCK cells was observed at 100 μM. Hemagglutination inhibition assay and docking experiment indicated that 11b might interfere with influenza virus infection by acting on HA protein. Broad-spectrum anti-influenza experiments showed 11b to be robustly potent against 5 different strains, including influenza A and B viruses, with IC50 values at the low-micromole level. Overall, this finding further extends the utility of OA-saccharide conjugates in anti-influenza virus drug design.
- Su, Yangqing,Meng, Lingkuan,Sun, Jiaqi,Li, Weijia,Shao, Liang,Chen, Kexuan,Zhou, Demin,Yang, Fan,Yu, Fei
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- AuBr3-catalyzed azidation of per-O-acetylated and per-O-benzoylated sugars
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Herein we report, for the first time, the successful anomeric azidation of per-O-acetylated and per-O-benzoylated sugars by catalytic amounts of oxophilic AuBr3 in good to excellent yields. The method is applicable to a wide range of easily accessible per-Oacetylated and per-O-benzoylated sugars. While reaction with per-O-acetylated and per-O-benzoylated monosaccharides was complete within 1-3 h at room temperature, the per-O-benzoylated disaccharides needed 2-3 h of heating at 55°C.
- Rajput, Jayashree,Hotha, Srinivas,Vangala, Madhuri
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p. 682 - 687
(2018/03/30)
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- Synthesis and anti-cancer activities of new sulfonamides 4-substituted-triazolyl nucleosides
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Nucleoside analogues are among the most known drugs commonly used in antiviral and anticancer chemotherapies. Among them, those featuring a five-membered ring nucleobase are of utmost interest such as the anti-cancer agent AICAR or the anti-viral drug ribavirin. Despite its low activity in vitro in different cell lines, AICAR is under clinical development for several pathologies, thanks to its original mode of action. Indeed, AICAR induced autophagy cell death and is able, following this mechanism, to circumvent resistance to apoptotic drugs including kinase inhibitors currently on the market. To improve the activity of AICAR, we report herein an efficient synthesis of new series of sulfonamide-4-substituted-1,2,3-triazolyl nucleosides using a Cu-catalyzed 1,3-dipolar cycloaddition. All these molecules have been fully characterized and evaluated against two aggressive tumor cell lines, RCC4 and MDA-MB-231. Among them, nucleoside analogue 5i belonging to the ribose series was found to be 19 to 66-fold more active than AICAR. Western blot analyses on RCC4 cells showed that 5i displayed an interesting mode of action by inducing both apoptosis and autophagy cell death, making therefore this class of molecules highly promising for further hit-to-lead optimization.
- Alaoui, Soukaina,Dufies, Maeva,Driowya, Mohsine,Demange, Luc,Bougrin, Khalid,Robert, Guillaume,Auberger, Patrick,Pagès, Gilles,Benhida, Rachid
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supporting information
p. 1989 - 1992
(2017/04/10)
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- Synthesis of new saccharide azacrown cryptands
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Abstract New cryptands including bis-azacrown and saccharidic moieties in their structure were prepared in several steps by applying Staudinger-aza-Wittig reaction (SAW). Syntheses have been started from cheap, easily available commercial compounds such as D-glucose, D-cellobiose and D-lactose subsequently transformed into their derivatives in fairly good yields (60-65%) and suitable to give desired final cryptands by direct SAW coupling reactions.
- Pintal, Michalina,Charbonniere-Dumarcay, Florence,Marsura, Alain,Porwański, Stanis?aw
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- Supramolecular stacking motifs in the solid state of amide and triazole derivatives of cellobiose
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1-Acetamido-1-deoxy-(4-O-β-d-glucopyranosyl-β-d-glucopyranose) (5) and 1-deoxy-1-(4-phenyl-1,2,3-triazolyl)-(4-O-β-d-glucopyranosyl- β-d-glucopyranose) (7) were synthesised from 1-azido-1-deoxy-(4-O-β-d- glucopyranosyl-β-d-glucopyranose) (2) and crystalli
- Hayes, John A.,Eccles, Kevin S.,Coles, Simon J.,Lawrence, Simon E.,Moynihan, Humphrey A.
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- Exploring the effect of bioisosteric replacement of carboxamide by a sulfonamide moiety on N-glycosidic torsions and molecular assembly: Synthesis and x-ray crystallographic investigation of n-(β- D -glycosyl)sulfonamides as n-glycoprotein linkage region analogues
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N-Glycoprotein linkage region constituents, 2-acetamido-2-deoxy-β-D- glucopyranose (GlcNAc) and asparagine (Asn) are conserved among all the eukaryotes. To gain a better understanding for nature's choice of GlcNAcβAsn as linkage region constituents and inter- and intramolecular carbohydrate-protein interactions, a detailed systemic structural study of the linkage region conformation is essential. Earlier crystallographic studies of several N-(β-glycopyranosyl)alkanamides showed that N-glycosidic torsion, φN, is influenced to a larger extent by structural variation in the sugar part than that of the aglycon moiety. To explore the effect of the bioisosteric replacement of a carboxamide group by a sulfonamide moiety on the N-glycosidic torsions as well as on molecular assembly, several glycosyl methanesulfonamides and glycosyl chloromethanesulfonamides were synthesized as analogues of the N-glycoprotein linkage region, and crystal structures of seven of these compounds have been solved. A comparative analysis of this series of crystal structures as well as with those of the corresponding alkanamido derivatives revealed that N-glycosidic torsion, φN, does not alter significantly. Methanesulfonamido and chloromethanesulfonamido derivatives of GlcNAc display a different aglycon conformation compared to other sulfonamido analogues. This may be due to the cumulative effect of the direct hydrogen bonding between N1 and O1′ and C-H×××O interactions of the aglycon chain, revealing the uniqueness of the GlcNAc as the linkage sugar. Unique molecular assembly motif of GlcNAc: The different aglycon conformations of methanesulfonamido and chloromethanesulfonamido derivatives of GlcNAc as compared to other sulfonamido analogues is a unique feature of their molecular assembly. This could be due to the cumulative effect of the direct hydrogen bonding between N1 and O1′ and C-H×××O interactions of the aglycon chain. Copyright
- Srivastava, Amrita,Varghese, Babu,Loganathan, Duraikkannu
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p. 17720 - 17732
(2014/01/17)
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- Supramolecular hydrogels based on glycoamphiphiles: Effect of the disaccharide polar head
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Supramolecular hydrogelators based on amphiphilic glycolipids have been prepared by clicking different sugar polar heads to a hydrophobic linear chain by copper(I)-catalyzed azide-alkyne [3 + 2] cycloaddition. The influence of the sugar polar head on the gelation properties in water has been studied, and the liquid crystalline properties of the amphiphilic materials have also been characterized. Stable hydrogels at room temperature have been obtained and the fibrillar supramolecular structures formed by the self-assembly have been studied by different microscopic techniques on the dried gel (xerogel) and hydrated conditions in order to characterize the micro- and nanostructures. Self-assembly gives rise to supramolecular ribbons with a torsion that is related to a chiral supramolecular arrangement of amphiphiles. The formation of an opposite helical arrangement of the ribbons has been found to depend on the sugar polar head. This fact was confirmed by circular dichroism (CD).
- Clemente, Maria J.,Romero, Pilar,Oriol, Luis,Fitremann, Juliette,Serrano, Jose L.
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p. 3847 - 3858,12
(2020/09/16)
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- Tandem staudinger-aza-Wittig templated reaction: De novo synthesis of sugar-ureido cryptands
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A templated Staudinger-aza-Wittig tandem reaction selectively affords in one step a monocellobiosyl[bis(ureido)]di- azacrown cryptand and a bis(cellobiosyl)tetraureido[bis(di- azacrown)] cryptand. Formation of each type of cryptand was under control by Na
- Porwanski, Stanislaw,Marsura, Alain
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supporting information; experimental part
p. 2047 - 2050
(2009/09/06)
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- Conjugation of 2-(1′-hexyloxyethyl)-2-devinylpyropheophorbide-a (HPPH) to carbohydrates changes its subcellular distribution and enhances photodynamic activity in vivo
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The carbohydrate moieties on conjugating with 3-(1′-hexyloxyethyl)-3- devinyl pyropeophorbide-α (HPPH) altered the uptake and intracellular localization from mitochondria to lysosomes. In vitro, HPPH-Gal 9 PDT showed increased PDT efficacy over HPPH-PDT as detectable by the oxidative cross-linking of nonphosphorylated STAT3 and cell killing in ABCG2-expressing RIF cells but not in ABCG2-negative Colon26 cells. This increased efficacy in RIF cells could at least partially be attributed to increased cellular accumulation of 9, suggesting a role of the ABCG2 transporter for which HPPH is a substrate. While such differences in the accumulation in HPPH derivatives by tumor tissue in vivo were not detectable, 9 still showed an elevated light dose-dependent activity compared to HPPH in mice bearing RIF as well as Colon26 tumors. Further optimization of the carbohydrate conjugates at variable treatment parameters in vivo is currently underway.
- Zheng, Xiang,Morgan, Janet,Pandey, Suresh K.,Chen, Yihui,Tracy, Erin,Baumann, Heinz,Missert, Joseph R.,Batt, Carrie,Jackson, Jennifer,Bellnier, David A.,Henderson, Barbara W.,Pandey, Ravindra K.
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experimental part
p. 4306 - 4318
(2010/03/04)
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- Synthesis of α- and β-glycosyl isothiocyanates via oxazoline intermediates
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(Chemical Equation Presented) A practical synthesis of acylated glycosyl isothiocyanates from sugar oxazolines, by reaction with thiophosgene, is reported. In the absence of any additive, the reaction is governed by the reverse anomeric effect, leading to
- Blanco, Jose L. Jimenez,Sylla, Balla,Mellet, Carmen Ortiz,Fernandez, Jose M. Garcia
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p. 4547 - 4550
(2008/02/05)
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- Dendrimers multivalently substituted with active groups
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The present invention relates to dendrimers being multivalently substituted with active groups, as well as to processes for the preparation thereof and to the use of such multivalent dendrimers. The active compounds encompass peptides, including oligopeptides up to entire proteins, carbohydrates and pharmaceutically active drug molecules. Active compounds are chemoselectively bound to the dendrimer periphery using a cycloaddition reaction (also termed as "click" reaction) between an alkyne group and either an azide or a nitrile oxide, leading to a 1,4-disubstituted 1,2,3-triazole or a 1,4-disubstituted 1,2-oxazole bridging unit. Such reaction is catalyzed by Cu(I) compounds. Microwave irradiation improves the efficiency of the click reaction.
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Page/Page column 9-10; 14
(2008/06/13)
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- Total synthesis of dapiramicin B
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The first total synthesis of dapiramicin B, a nucleoside antibiotic, is described. The characteristic N-glycoside linkage in dapiramicin B was effectively constructed by way of the Pd-catalyzed coupling reaction of a heptopyranosylamine with a bromopyrrol
- Ohno, Hiroyuki,Terui, Takashi,Kitawaki, Takafumi,Chida, Noritaka
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p. 5747 - 5750
(2007/10/03)
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- High-yielding microwave-assisted synthesis of triazole-linked glycodendrimers by copper-catalyzed [3+2] cycloaddition
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A facile and high-yielding synthesis of multivalent 1,4-disubstituted 1,2,3-triazole-linked glycodendrimers is described. Azido carbohydrates are linked by a CuI-catalyzed [3+2] cycloaddition reaction to dendritic acetylenes using microwave irradiation. Wiley-VCH Verlag GmbH & Co. KGaA, 2005.
- Joosten, John A. F.,Tholen, Niels T. H.,Ait El Maate, Fatna,Brouwer, Arwin J.,Wilma Van Esse,Rijkers, Dirk T. S.,Liskamp, Rob M. J.,Pieters, Roland J.
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p. 3182 - 3185
(2007/10/03)
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- General methods for the synthesis of glycopyranosyluronic acid azides
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Per-O-acetylated D-glycopyranoses derived from both mono- and disaccharides were first converted to glycosyl iodides and subsequently reacted with an azide source to achieve the stereoselective synthesis of β-D-glycosyl azides after deacetylation. Low-temperature (4°C) TEMPO oxidation of the monosaccharides provided the corresponding uronic acids, which were purified as the free acids. Oxidation of the lactosyl- and cellobiosyl azides resulted in diacid formation. However, 4′,6′-O-benzylidene protection enabled selective oxidation of the C-6 hydroxyl. 2-Acetamido-2-deoxy-D-glycopyranosyl azides were also prepared and converted to uronic acids completing the library synthesis.
- Ying, Laiqiang,Gervay-Hague, Jacquelyn
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p. 835 - 841
(2007/10/03)
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- A simple and convenient synthesis of glycosyl azides
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Treatment of glycosyl halides with NaN3 in aqueous acetone or acetonitrile is a convenient method for the stereoselective synthesis of 1,2- transper-O-acetyl-glycosyl azides.
- Ibatullin, Farid M.,Shabalin, Konstantin A.
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p. 2819 - 2823
(2007/10/03)
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- The Use of Tetramethylguanidinium Azide in Non-halogenated Solvents Avoids Potential Explosion Hazards
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Tetramethylguanidinium azide was used in the quantitative conversion of glycosyl halides 1 - 5 to the corresponding glycosyl azides 10 -14.The stereoselective reactions occurred with complete inversion at the anomeric centers.The titled reagent was also employed in the selective synthesis of pseudoglycosyl azide 16 and two steroidal azides 17 and 18.All reactions were carried out in nonhalogenated solvents to avoid potential explosion hazards.
- Li, C.,Shih, Tzenge-Lien,Jeong, Jae Uk,Arasappan, Ashok,Fuchs, P. L.
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p. 2645 - 2646
(2007/10/02)
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- Tetramethylguanidinium azide as a new reagent for the stereoselective synthesis of glycosyl azides
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Tetramethylguanidium azide was used in the quantitative conversion of glycosyl halides 1 - 6 to the corresponding glycosyl azides 7 - 12. The stereoselective reactions occurred with complete inversion at the anomeric centers.
- Li,Arasappan,Fuchs
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p. 3535 - 3538
(2007/10/02)
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- Synthesis of the Anomers of Hepta-O-acetylcellobiosyl, -lactosyl, -maltosyl, and -melibiosyl Azide
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Synthesis and characterization by 13C-NMR spectroscopy of the O-acetylated 1,2-cis- and 1,2-trans azides of cellobiose, lactose, maltose, and melibiose have been accomplished. 1,2-trans Azides 1c, 2b-4b result from the stannic chloride catalyzed reaction of the β-octa-O-acetates 1a-4a with trimethylsilyl azide, whereas the β-chlorohepta-O-acetyldisaccharides 1d, 2c-4c afford, in an SN2 reaction in HMPT with lithium azide, the hitherto inaccessible 1,2-cis azides 1e, 2d-4d.
- Peto, Csaba,Batta, Gyula,Gyoergydeak, Zoltan,Sztaricskai, Ferenc
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p. 505 - 507
(2007/10/02)
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