- 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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- 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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- 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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- 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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- Synthesis of a 1,3 β-glucan hexasaccharide designed to target vaccines to the dendritic cell receptor, Dectin-1
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Transformation of 3-O-benzyl-1,2:5,6-di-O-isopropylidene-α-d-glucofuranose into 2,4,6-tri-O-benzoyl-3-O-benzyl glucopyranosyl imidate proceeded efficiently via crystalline benzyl and per-benzoylated derivatives. This imidate glycosylated di-O-isopropylidene-α-d-glucofuranose in high yield and glycosylation of the disaccharide after removal of the 3′-O-benzyl ether afforded the β1,3 linked trisaccharide in excellent yield. Di- and trisaccharides imidates were readily prepared from the furanose terminated glycosylation products but both were unreactive in glycosylation reaction with the debenzylated di- and trisaccharide alcohols. The 3′-O-benzyl perbenzoylated disaccharide pyranose derivative could be selectively debenzoylated and converted to the corresponding perbenzoylated 4,6:4′,6′-di-O-benzylidene derivative. Lewis acid catalyzed glycosidation gave the selectively protected disaccharide ethylthioglycoside in good overall yield. Glycosidation of this thioglycoside donor with 5-methoxycarbonylpentanol gave the disaccharide tether glycoside and after catalytic removal of benzyl ether the resulting disaccharide alcohol was glycosylated by the thioglycoside in a 2+2 reaction to yield a tetrasaccharide. Repetition of selective deprotection of the terminal 3-O-benzyl ether followed by glycosylation by the disaccharide thioglycoside gave a protected hexasaccharide. Hydrogenolysis of this hexasaccharide followed by transesterification and second hydrogenolysis to remove a residual benzyl group gave the target hexasaccharide glycoside 1 as a Dectin-1 ligand functionalized to permit covalent attachment to glycoconjugate vaccines and thereby facilitate improved antigen processing by dendritic cells.
- Elsaidi, Hassan R.H.,Paszkiewicz, Eugenia,Bundle, David R.
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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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- 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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- 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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supporting information; scheme or table
p. 2952 - 2955
(2012/07/30)
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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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- 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 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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- 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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- 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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- Method of producing α-dihydropolyprenyl monophosphates
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A method of producing α-dihydropolyprenyl monophosphates from α-dihydropolyprenols through α-dihydropolyprenyl dichlorophosphates in good yield and with ease is provided. A method of producing α-dihydropolyprenyl dichlorophosphates which are intermediate compounds useful for the first-mentioned method is also provided.
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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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