- Carbon tetrachloride-free allylic halogenation-mediated glycosylations of allyl glycosides
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The allylic bromination of allyl glycosides is conducted using NBS/AIBN reagents in (EtO)2CO and PhCF3 solutions, without using CCl4 as a solvent. The activated mixed halo-allyl glycosides led to glycosylations, mediated by a triflate, in a latent-active
- Das, Anupama,Jayaraman, Narayanaswamy
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p. 9318 - 9325
(2021/11/13)
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- GLUCOSE-RESPONSIVE INSULIN CONJUGATES
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Glucose-responsive insulin conjugates that contain one or more trisaccharides are provided. Such insulin conjugates may display a pharmacokinetic (PK) and/or pharmacodynamic (PD) profile that is responsive to the systemic concentrations of a saccharide such as glucose or alpha-methylmannose, even when administered to a subject in need thereof in the absence of an exogenous multivalent saccharide-binding molecule.
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Page/Page column 119; 141
(2021/02/05)
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- Delta-oleanolic acid saponin compound and medical application thereof
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The invention discloses a delta-oleanolic acid saponin compound and medical application thereof. The delta-oleanolic acid saponin compound is a compound with a structural formula shown as a formula (I), and pharmaceutically acceptable salt or ester or pro
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Paragraph 0074-0076; 0078
(2020/12/31)
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- Glycosylation with 3,5-Dimethyl-4-(2′-phenylethynylphenyl)phenyl (EPP) Glycosides via a Dearomative Activation Mechanism
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A highly effective and versatile glycosylation method is developed, which uses 3,5-dimethyl-4-(2′-phenylethynylphenyl)phenyl (EPP) glycosides as donors and NIS/TMSOTf as promoter and proceeds via an unprecedented dearomative activation mechanism.
- Hu, Zhifei,Tang, Yu,Yu, Biao
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supporting information
p. 4806 - 4810
(2019/03/26)
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- Lewis acid promoted anomerisation of alkyl O- and S-xylo-, arabino- and fucopyranosides
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Pentopyranoside and 6-deoxyhexopyranosides, such as those from D-xylose, L-arabinose and L-fucose are components of natural products, oligosaccharides or polysaccharides. Lewis acid promoted anomerisation of some of their alkyl O- and S-glycopyranosides i
- Doyle, Lisa M.,Meany, Fiach B.,Murphy, Paul V.
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supporting information
p. 85 - 94
(2018/12/05)
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- The dehydroepiandrosterone and dehydroepiandrosterone alkone glycosylation derivative and its preparation method and application
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The invention discloses epiandrosterone glycosylation derivatives and dehydrogenated epiandrosterone glycosylation derivatives, and a preparation method thereof. The preparation method comprises the following steps: respectively carrying out coupling reac
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Paragraph 0041; 0046
(2017/04/28)
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- 3-(Dimethylamino)-1-propylamine: A cheap and versatile reagent for removal of byproducts in carbohydrate chemistry
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Inexpensive 3-(dimethylamino)-1-propylamine (DMAPA) was found to be effective in anomeric deacylation reactions giving 1-O deprotected sugars in high yield as precursors for the formation of imidate glycosyl donors. DMAPA was also found to be useful for removing excess reagents such as benzoyl chloride, tosyl chloride, and 2,2,2-trifluoro-N-phenylacetimidoyl chloride. The deacylation reaction could be conducted in moist THF and did not require chromatographic purification since an acidic wash was sufficient to remove excess reagent and the formed byproduct.
- Andersen, Sofie Meng,Heuckendorff, Mads,Jensen, Henrik H.
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supporting information
p. 944 - 947
(2015/04/14)
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- 2′-Deoxy-2′,2′-difluorothymidine analogues for radiolabeling with fluorine-18 and other biomedical applications
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Novel 2′-deoxy-2′,2′-difluorothymidine analogues with potential applications as antiviral, cytotoxic and cancer imaging agents have been synthesized. Introduction of the hydroxymethyl functionality at the 5-position of 2′-deoxy-2′,2′-difluoruridine provided a key intermediate with a suitable synthetic handle for the generation of these nucleoside derivatives.
- Doepner, Andreas M.,Aboagye, Eric O.,Barrett, Anthony G.M.
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p. 3293 - 3297
(2015/03/04)
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- TIMOSAPONIN COMPOUNDS
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Provided herein are timosaponin compounds of Frmula I, II, IIΙ, I', II' and IIΙ', pharmaceutical compositions comprising the coumpounds, and processes of preparation thereof. Also provided are uses of said timosaponin compounds for preparing medicament for the treatment of diseases associated with beta-amyloid in hosts or subjects in need thereof.
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- Cross metathesis assisted solid-phase synthesis of glycopeptoids
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A solid-phase synthesis of glycopeptoids was explored through olefin cross metathesis (CM). Peptoids and sugar derivatives with appropriate olefin moieties were coupled in the presence of an olefin metathesis catalyst to afford glycopeptoids in good yield
- Khan, Sharaf Nawaz,Kim, Arim,Grubbs, Robert H.,Kwon, Yong-Uk
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p. 2952 - 2955
(2012/07/30)
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- Saccharide-modified nanodiamond conjugates for the efficient detection and removal of pathogenic bacteria
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The detection and removal of bacteria, such as E. coli in aqueous environments by using safe and readily available means is of high importance. Here we report on the synthesis of nanodiamonds (ND) covalently modified with specific carbohydrates (glyco-ND) for the precipitation of type 1 fimbriated uropathogenic E. coli in solution by mechanically stable agglutination. The surface of the diamond nanoparticles was modified by using a Diels-Alder reaction followed by the covalent grafting of the respective glycosides. The resulting glyco-ND samples are fully dispersible in aqueous media and show a surface loading of typically 0.1 mmol g-1. To probe the adhesive properties of various ND samples we have developed a new sandwich assay employing layers of two bacterial strains in an array format. Agglutination experiments in solution were used to distinguish unspecific interactions of glyco-ND with bacteria from specific ones. Two types of precipitates in solution were observed and characterized in detail by light and electron microscopy. Only by specific interactions mechanically stable agglutinates were formed. Bacteria could be removed from water by filtration of these stable agglutinates through 10 μm pore-size filters and the ND conjugate could eventually be recovered by addition of the appropriate carbohydrate. The application of glycosylated ND allows versatile and facile detection of bacteria and their efficient removal by using an environmentally and biomedically benign material. Copyright
- Hartmann, Mirja,Betz, Patrick,Sun, Yuchen,Gorb, Stanislav N.,Lindhorst, Thisbe K.,Krueger, Anke
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supporting information; experimental part
p. 6485 - 6492
(2012/06/16)
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- 1,2-Trans-selective synthesis of glycosyl boranophosphates and their utility as building blocks for the synthesis of phosphodiester-linked disaccharides
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Figure Presented A highly 1,2-trans-selective synthesis of glycosyl boranophosphate derivatives by glycosylation of dimethyl boranophosphate with glycosyl iodides was developed. A study on the reaction mechanism indicated that the stereoselectivity of the
- Sato, Kazuki,Oka, Natsuhisa,Fujita, Shoichi,Matsumura, Fumiko,Wada, Takeshi
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supporting information; experimental part
p. 2147 - 2156
(2010/06/17)
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- Synthesis of phalluside-1 and Sch II using 1,2-metallate rearrangements
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(4E,8E,10E)-9-Methyl-4,8,10-sphingatrienine, a core component of marine sphingolipids, was synthesised for the first time using a copper(i)-mediated 1,2-metallate rearrangement of a lithiated glycal as a key step. It was converted to phalluside-1, a cereb
- Black, Fiona J.,Kocienski, Philip J.
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supporting information; scheme or table
p. 1188 - 1193
(2010/06/15)
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- Synthesis of fluorescein-labelled O-mannosylated peptides as components for synthetic vaccines: Comparison of two synthetic strategies
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Mannose-binding proteins on the surface of antigen-presenting cells (APCs) are capable of recognizing and internalizing foreign agents in the early stages of immune response. These receptors offer a potential target for synthetic vaccines, especially vaccines designed to stimulate T cells. We set out to synthesize a series of fluorescein-labelled O-mannosylated peptides using manual solid phase peptide synthesis (SPPS) on pre-loaded Wang resin, in order to test their ability to bind mannose receptors on human APCs in vitro. A flexible and reliable method for the synthesis of fluorescein-labelled O-mannosylated glycopeptides was desired in order to study their lectin-binding properties using flow cell cytometry. Two synthetic strategies were investigated: incorporation of a fluorescein label into the peptide chain via a lysine side chain ε-amino group at the final stage of standard Fmoc solid phase peptide synthesis or attachment of the fluorescein label to the Nα- amino group of a lysine with further incorporation of a mannosylated peptide unit through the side chain Nε-amino group. The latter strategy proved more effective in that it facilitated SPPS by positioning the growing mannosylated peptide chain further removed from the fluorescein label. The Royal Society of Chemistry 2008.
- Brimble, Margaret A.,Kowalczyk, Renata,Harris, Paul W. R.,Dunbar, P. Rod,Muir, Victoria J.
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p. 112 - 121
(2008/09/20)
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- Synthesis of 131I-labeled glucose-conjugated inhibitors of 06-methylguanine-DNA methyltransferase (MGMT) and comparison with nonconjugated inhibitors as potential tools for in vivo MGMT imaging
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O6-Substituted guanine derivatives are powerful agents used for tumor cell sensitization by inhibition of the DNA repair enzyme O 6-methylguanine-DNA methyltransferase (MGMT). To provide targeted accumulation of MGMT inhibitors in tu
- Mühlhausen, Ute,Schirrmacher, Ralf,Piel, Markus,Lecher, Bernd,Briegert, Manuela,Piee-Staffa, Andrea,Kaina, Bernd,R?sch, Frank
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p. 263 - 272
(2007/10/03)
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- Chloramine-T-mediated chemoselective hydrolysis of thioglycosides into glycosyl hemiacetals under neutral conditions
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A metal-free, mild, efficient and chemoselective hydrolysis of several thioalkylglycosides (1) into their corresponding 1-hydroxy sugars (2) using sodium N-chloro-p-toluenesulfonamide trihydrate (chloramine-T) without affecting other functional groups is reported.
- Misra, Anup Kumar,Agnihotri, Geetanjali
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p. 885 - 890
(2007/10/03)
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- A new, efficient glycosylation method for oligosaccharide synthesis under neutral conditions: Preparation and use of new DISAL donors
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Efficient, stereoselective glycosylation methods are required for the synthesis of complex oligosaccharides as tools in glycobiology. All glycosylation methods, which have found wide acceptance, rely on Lewis acid activation of glycosyl donors prior to glycosylation. Here, we present a new and efficient method for glycosylation under neutral or mildly basic conditions. Glycosides of methyl 2-hydroxy-3,5-dinitrobenzoate (DISAL) and its para regioisomer, methyl 4-hydroxy-3,5-dinitrobenzoate, were prepared by nucleophilic aromatic substitution. In a first demonstration of their potential as glycosyl donors, stereospecific glycosylation of methanol was achieved. In the glycosylation of more hindered alcohols, the β-donor proved more reactive, and α-glucosides were predominantly formed. Glycosylation of protected monosaccharides, with free 6-0H or 3-OH, proceeded smoothly in 1-methyl-2-pyrrolidinone (NMP) at 40-60 °C in the absence of Lewis acids and bases in good to excellent yields. Glycosylation of 3-OH gave the α-linked disaccharide only.
- Petersen,Jensen
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p. 6268 - 6275
(2007/10/03)
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- A new, scalable preparation of a glucopyranosylidene-spiro- thiohydantoin: One of the best inhibitors of glycogen phosphorylases
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Benzobromo-glucose was converted into per-O-benzoylated β-D- glucopyranosyl cyanide by mercury(II) cyanide in nitromethane. Partial hydrolysis of the nitrile with hydrogen bromide in acetic acid gave per-O- benzoylated C-(β-D-glucopyranosyl)formamide. Photobromination using bromine in carbon tetrachloride, chloroform, or dichloromethane gave the corresponding per-O-benzoylated 1-bromo-1-deoxy-β-D-glucopyranosyl cyanide and C-(1-bromo-1-deoxy-β-D-glucopyranosyl)formamide. Reaction of the latter with ammonium thiocyanate in nitromethane gave the per-O-benzoylated C-6S configured glucopyranosylidene-spiro-thiohydantoin together with a small amount of the per-O-benzoylated C-(1-hydroxy-β-D-glucopyranosyl)formamide. Debenzoylation of the spiro-thiohydantoin with sodium methoxide in methanol gave gram amounts of the title inhibitor. The described sequence should be suitable for scaling up and the target compound can be prepared in ~30% overall yield starting from D-glucose. (C) 2000 Elsevier Science Ltd.
- Somsak, L.Aszlo,Nagy, Veronika
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p. 1719 - 1727
(2007/10/03)
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- The reaction of penta-O-benzoyl-D-glucopyranose with piperidine: Characterization of the products isolated and study of the reaction mechanism
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The reaction of penta-O-benzoyl-D-glucopyranose with piperidine gave N-(2,3,6-tri-O-benzoyl-β-D-glucopyranosyl)piperidine (44.1%), N-(2,4,6-tri-O-benzoyl-β-D-glucopyranosyl)piperidine (1.5%), N-benzoylpiperidine and piperidinium benzoate (approx 1 mol of each of these two products per mol of substrate). When several penta-O-benzoyl-D-glucopyranoses containing selectively 14C-labeled benzoyloxy groups were submitted to the same reaction, it was found that N-benzoylpiperidine is formed at the expense of benzoyloxy-C-1, piperidinium benzoate arises mainly from benzoyloxy-C-2, and the benzoyloxy groups originally attached to C-3, C-4, and C-6 remain in the major product of the reaction. These results demonstrate that the first compound produced in the reaction is N-(3,4,6-tri-O-benzoyl-β-D-glucopyranosyl)piperidine, which could not be isolated because it undergoes two consecutive benzoyl migrations: a migration from O-3 to O-2 to give the 2,4,6-tri-O-benzoate, followed by a migration from O-4 to O-3 to afford the 2,3,6-tri-O-benzoate. A mechanism to explain the formation of piperidinium benzoate from benzoyloxy-C-2 of penta-O-benzoyl-D-glucopyranose is proposed. Copyright (C) 1999 Elsevier Science Ltd.
- Salinas, Amelia E.
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- A novel and efficient deprotection of the allyl group at the anomeric oxygen of carbohydrates
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Perfluoroalkylation with perfluoroalkyl iodide under sodium dithionite and sodium bicarbonate in acetonitrile/water followed by elimination in the presence of zinc powder and ammonium chloride in ethanol was disclosed to be an extremely mild and efficient procedure for deprotection of the anomeric allyl group of carbohydrates.
- Yu, Biao,Zhang, Jianbo,Lu, Shoufu,Hui, Yongzheng
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- Application of the hydrogenphosphonate approach in the synthesis of glycosyl phosphosugars linked through secondary hydroxyl groups
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The hydrogenphosphonate approach has been used in syntheses of methyl α-D-mannopyranoside 2-, 3-, and 4-(α-D-mannopyranosyl phosphate), benzyl β-D-galactopyranoside 2-(α-D-mannopyranosyl phosphate), and methyl β-D-galactopyranoside 4-(α-D-mannopyranosyl phosphate).Condensation of 2,3,4,6-tetra-O-benzyl- or 2,3,4,6-tetra-O-benzoyl-α-D-mannopyranosyl hydrogenphosphonate with suitable, partially acylated monohydroxy derivatives in the presence of Me3CCOCl, followed by oxidation of the resulting hydrogenphosphonate diesters with iodine, gave the O-protected phosphate diesters in yields of 67-87percent.Deprotection then gave the glycosyl phosphosugars.
- Nikolaev, Andrey V.,Ivanova, Irena A.,Shibaev, Vladimir N.,Kochetkov, Nikolay K.
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- AMMONOLYSIS OF PENTA-O-BENZOYL-α-D-GLUCOPYRANOSE IN AN APROTIC MEDIUM. CHARACTERIZATION OF THE PRODUCTS ISOLATED, AND CONFORMATIONAL ANALYSIS OF ELEVEN N-BENZOYL-D-GLUCOFURANOSYLAMINE DERIVATIVES
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The reaction of penta-O-benzoyl-α-D-glucopyranose with chloroform-1,4-dioxane-liquid ammonia gave 1,1-bis(benzamido)-6-O-benzoyl-1-deoxy-D-glucitol (29.0percent), three partially benzoylated derivatives of N-benzoyl-α-D-glucofuranosylamine (23.6percent), a small proportion of N-benzoyl-di-O-benzoyl-β-D-glucofuranosylamine (0.2percent), and four partially benzoylated derivatives of α-D-glucopyranose (9.9percent).The structures of the hitherto-unknown products, and their anomeric configurations, were established by chemical and spectroscopic methods.The conformations in solution of both anomers of N-benzoyl-D-glucofuranosylamine, their partially benzoylated derivatives isolated from the ammonolysis reaction, and the per-O-acetyl derivatives of the various compounds were analyzed by (1)H-n.m.r.spectroscopy.
- Salinas, Amelia E.,Sproviero, Jorge F.,Deulofeu, Venancio
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- A Facile Regioselective 1-O-Deacylation of Peracylated Glycopyranoses
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The regioselective deacylation of peracylated glycopyranoses 1-5 with ammonia in a polar aprotic solvent to the corresponding α-1-OH sugar derivatives 6-10 in total or high stereoselectivity is described.
- Fiandor, J.,Garcia-Lopez, M. T.,Heras, F. G. De Las,Mendez-Castrillon, P. P.
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p. 1121 - 1123
(2007/10/02)
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