- 6-Azido-6-deoxy-l-idose as a Hetero-Bifunctional Spacer for the Synthesis of Azido-Containing Chemical Probes
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The design of 6-azido-6-deoxy-l-idose for use as a hetero-bifunctional spacer is reported. The hemiacetal at one terminus is an equivalent of an aldehyde and can react with nucleophiles, such as amino groups and electron-rich aromatics. The azido group at the other terminus bio-orthogonally undergoes a Hüisgen [3+2] cycloaddition with an acetylene. The idose derivative exhibited a higher level of reactivity towards oxime formation than a corresponding glucose derivative. The13C NMR spectrum of the uniformly13C-labeled 6-azido-idose indicated that the acyclic forms of the sugar totaled 0.3 % of all the isomers, whereas those of glucose totaled 0.01 %. The larger population of the acyclic forms of the idose derivative would result in higher reactivity towards electrophilic addition in comparison with glucose derivatives. Finally, we prepared a C-idosyl epigallocatechin gallate (EGCG) that bears an azido group through C-glycosylation of EGCG with 6-azido-idose. This glycosyl form of the C-idosyl EGCG exhibited a cytotoxicity against U266 cells that was comparable to that of EGCG. These results suggested that the EGCG derivative could be used as an effective chemical probe for the elucidation of EGCG biological functions.
- Hamagami, Hiroki,Kumazoe, Motofumi,Yamaguchi, Yoshiki,Fuse, Shinichiro,Tachibana, Hirofumi,Tanaka, Hiroshi
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supporting information
p. 12884 - 12890
(2016/08/30)
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- Curdlan as a polymeric starting material to access C6-modified glucose derivatives
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We evaluated the potential of a linear β-1,3-glucan (curdlan) as a starting material to access C6-modified glucose derivatives and found that 6-bromo-6-deoxyglucose, 6-azide-6-deoxyglucose, and 6-acetamido-6-deoxyglucose could be readily prepared from curdlan through its C6-selective and quantitative modifications and subsequent acid-catalyzed hydrolysis.
- Miyazawa, Tomoyuki,Abe, Haruka,Suzuki, Takayuki,Togashi, Yosuke,Koshiji, Kazuhiro,Nonaka, Yuki,Hasegawa, Teruaki
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p. 252 - 266
(2014/07/07)
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- Model for antibiotic optimization via neoglycosylation: Synthesis of liponeoglycopeptides active against VRE
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The neoglycosylation of a methoxyamine-appended vancomycin aglycon with all possible N′-decanoylglucopyranose and N′-biphenoylglucopyranose regioisomers led to the production of a focused set of liponeoglycopeptide variants in good yields and with excellent stereoselectivity. High-throughput antibacterial assays employing a unique set of vancomycin-resistant Enterococci faecalis and Enterococci faecium clinical isolates revealed that the nature and regiochemistry of glycosyl lipidation modulated vancomycin-resistent Enterococci potency. In contrast to prior work with lipoglycopeptides, this study reveals the glucose C3′ or C4′ as the optimal position for neoglycopeptide lipidation. This purely chemical method for the diversification of the glycolipid portion of lipoglycopeptide antibiotics is simple to perform on a large scale, requires minimal synthetic effort in sugar donor preparation, and provides access to highly active antibiotics that are not easily prepared by other state-of-the-art methods.
- Griffith, Byron R.,Krepel, Candace,Fu, Xun,Blanchard, Sophie,Ahmed, Aqeel,Edmiston, Charles E.,Thorson, Jon S.
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p. 8150 - 8155
(2008/02/11)
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- Novel drug delivery compositions
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The present invention provides for a novel molecules useful for delivery of compounds to a mammal, more particularly for the intracellular delivery of nucleotides, nucleotide analogues or compounds with a heterocyclic base. Also provided for are novel therapeutic complexes comprising novel molecules complexed with nucleotide analogues or heterogeneous or homogenous oligomers comprised of nucleotide analogues.
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Page/Page column 13
(2010/11/25)
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- The direct synthesis of 6-amino-6-deoxyaldonic acids as monomers for the preparation of polyhydroxylated nylon 6
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6-Azido-6-deoxy-d-galactitol and d-mannitol were obtained quantitatively via the reduction of the corresponding 6-azido-6-deoxy-d-hexono-1,4-lactones, and 6-azido-6-deoxy-d-glucitol was obtained by the reduction of 6-azido-6-deoxyglucose in good yields. The reduction of monoazidodeoxyhexitols by catalytic hydrogenation gave the monoaminohexitol analogues in 95-98% yields. Oxidation of these afforded the corresponding 6-amino-6-deoxy-d-aldonic acids in moderate yields. Alternatively, saponification of 6-azido-6-deoxy-d-hexonolactones gave 6-azido-6-deoxyaldonic acid salts which, after reduction followed by neutralization, led to the expected compounds in 82-88% overall yields.
- Chaveriat, Ludovic,Stasik, Imane,Demailly, Gilles,Beaupere, Daniel
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p. 1349 - 1354
(2007/10/03)
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- A general entry to linear, dendritic and branched thiourea-linked glycooligomers as new motifs for phosphate ester recognition in water
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A blockwise iterative synthetic strategy for the preparation of linear, dendritic and branched full-carbohydrate architectures has been developed by using sugar azido(carbamate) isothiocyanates as key templates; the presence of intersaccharide thiourea br
- Blanco, Jose L. Jimenez,Bootello, Purificacion,Mellet, Carmen Ortiz,Gallego, Ricardo Gutierrez,Fernandez, Jose M. Garcia
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- Enzymatic/chemical synthesis and biological evaluation of seven-membered iminocyclitols
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Several polyhydroxyperhydroazepines have been obtained either by chemoenzymatic or chemical synthesis. Condensation of (±)-3-azido-2-hydroxypropanaldehyde and dihydroxyacetone phosphate (DHAP) in the presence of a DHAP dependent aldolase followed by treat
- Morís-Varas, Francisco,Qian, Xin-Hua,Wong, Chi-Huey
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p. 7647 - 7652
(2007/10/03)
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- Thioureido-β-cyclodextrins as molecular carriers
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Alkyl, glycosyl and glycopeptidyl derivatives of 6I-deoxy-6I-thioureidocyclomaltoheptaose, prepared in high yield from either 6I-amino-6I-deoxycyclomaltoheptaose or the corresponding 6I-isithiocyanate
- Fernandez, Jose M. Garcia,Mellet, Carmen Ortiz,Maciejewski, Sylwester,Defaye, Jacques
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p. 2741 - 2742
(2007/10/03)
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- A Simple Convergent Synthesis of the Mannosidase Inhibitor 1-Deoxymannonojirimycin from Sucrose
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The glycosidase inhibitor 1-deoxymannonojirimycin (1,5-dideoxy-1,5-imino-D-mannitol) was synthesized in four simple steps from sucrose via 6,6'-diazido-6,6'-dideoxysucrose and 6-azido-6-deoxy-D-fructofuranose.The "isomeric ballast" of the sequence, 6-azido-6-deoxy-D-glucose, could be partially converted into 6-azido-6-deoxy-d-fructofuranose with the aid of glucose isomerase (E.C. 5.3.1.5) demonstrating a novel synthetic application of this enzyme.The sequence allows access to multigramm quantities of 1-deoxy-mannonojirimycin in over 30percent overall yield without the need for expensive reagents and protecting group manipulations.Key Words: 1-deoxymannonojirimycin, mannosidase inhibitor, glucose isomerase, sucrose, synthesis
- Raadt, Anna de,Stuetz, Arnold E.
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p. 189 - 192
(2007/10/02)
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- Fructose 1,6-Diphosphate Aldolase Catalyzed Stereoselective Synthesis of C-Alkyl and N-Containing Sugars: Thermodynamically Controlled C-C Bond Formations.
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Fructose 1,6-diphosphate aldolase catalyzed aldol condensations have been used in syntheses of several new N-containing and C-alkyl sugars on 4-20 mmol scales.The enzyme is highly specific for dihydroxyacetone phosphate as donor but accepts a number of achiral and chiral aldehydes (both D and L isomers) as acceptors.Due to the reversible nature of the aldol reaction, a thermodynamically controlled approach was employed for the syntheses in which racemic aldehydes were used as substrates and thermodynamically more stable products were preferentially produced.
- Durrwachter, John R.,Wong, Chi-Huey
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p. 4175 - 4181
(2007/10/02)
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- Facile Syntheses of Galacto- and Glucopyranosyl Azides Substituted at C-6
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Acetylated 6-chloro-, 6-bromo-, 6-iodo-, and 6-azido-6-deoxy-α-D-glucopyranosyl azides (26, 22, 17, 30), -β-D-glucopyranosyl azides (27, 23, 18, 31), -α-D-galactopyranosyl azides (28, 24, 19, 32), and -β-D-galactopyranosyl azides (29, 25, 20, 33) have been obtained by nucleophilic displacement reactions of the appropriate 6-O-(p-toluenesulfonates) 9-12.Hydrogen iodide elimination from the 6-iodo-6-deoxyglycosyl azides 17-20 by DBU or DBN leads to the hex-5-enopyranosyl azides with α-D-xylo (43), β-D-xylo (44), α-L-arabino (46), and β-L-arabino configuration.The. structures, anomeric configurations, and conformations of the products were determined by 1H-NMR spectroscopy
- Gyoergydeak, Zoltan,Szilagyi, Laszlo
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p. 235 - 242
(2007/10/02)
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