- Selective Secondary Face Modification of Cyclodextrins by Mechanosynthesis
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α-, β-, and γ-cyclodextrins (CDs) were modified on their secondary face by mechanosynthesis at room temperature using a laboratory-scale ball-mill. Mono-2-tosylated α-, β-, and γ-CDs were obtained in good yield from mixtures of native α-, β-, and γ-CDs, r
- Menuel, Stéphane,Doumert, Bertrand,Saitzek, Sébastien,Ponchel, Anne,Delevoye, Laurent,Monflier, Eric,Hapiot, Frédéric
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- Nickel Boride Catalyzed Reductions of Nitro Compounds and Azides: Nanocellulose-Supported Catalysts in Tandem Reactions
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Nickel boride catalyst prepared in situ from NiCl2 and sodium borohydride allowed, in the presence of an aqueous solution of TEMPO-oxidized nanocellulose (0.01 wt%), the reduction of a wide range of nitroarenes and aliphatic nitro compounds. Here we describe how the modified nanocellulose has a stabilizing effect on the catalyst that enables low loading of the nickel salt pre-catalyst. Ni-B prepared in situ from a methanolic solution was also used to develop a greener and facile reduction of organic azides, offering a substantially lowered catalyst loading with respect to reported methods in the literature. Both aromatic and aliphatic azides were reduced, and the protocol is compatible with a one-pot Boc-protection of the obtained amine yielding the corresponding carbamates. Finally, bacterial crystalline nanocellulose was chosen as a support for the Ni-B catalyst to allow an easy recovery step of the catalyst and its recyclability for new reduction cycles.
- Proietti, Giampiero,Prathap, Kaniraj Jeya,Ye, Xinchen,Olsson, Richard T.,Dinér, Peter
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supporting information
p. 133 - 146
(2021/11/04)
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- TBAF Effects 3,6-Anhydro Formation from 6-O-Tosyl Pyranosides
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3,6-Anhydro sugars are common structures in algal polysaccharides and occur in the furanodictine and sauropunol natural products. We have found that treatment of 6-O-tosylpyranosides with tetrabutylammonium fluoride provides a mild, high-yielding synthesis of 3,6-anhydro sugars. Using O-glycoside substrates, 3,6-anhydropyranosides are isolated and the use of N,O-dimethyl hydroxylamine glycosides yields 3,6-anhydrofuranosides. Applying this approach, concise synthetic routes to several 3,6-anhydro sugar natural products are reported, including furanodictine A and sauropunols A-D.
- Morrison, Zachary A.,Nitz, Mark
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supporting information
(2020/02/26)
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- Regioselective Sulfonylation/Acylation of Carbohydrates Catalyzed by FeCl3 Combined with Benzoyltrifluoroacetone and Its Mechanism Study
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A catalytic amount of FeCl3 combined with benzoyl trifluoroacetone (Hbtfa) (FeCl3/Hbtfa = 1/2) was used to catalyze sulfonylation/acylation of diols and polyols using diisopropylethylamine (DIPEA) or potassium carbonate (K2CO3) as a base. The catalytic system exhibited high catalytic activity, leading to excellent isolated yields of sulfonylation/acylation products with high regioselectivities. Mechanism studies indicated that FeCl3 initially formed [Fe(btfa)3] (btfa = benzoyl trifluoroacetonate) with twice the amount of Hbtfa under basic conditions in the solvent acetonitrile at room temperature. Then, Fe(btfa)3 and two hydroxyl groups of the substrates formed a five- or six-membered ring intermediate in the presence of the base. The subsequent reaction between the cyclic intermediate and a sulfonylation reagent led to the selective sulfonylation of the substrate. All key intermediates were captured in the high-resolution mass spectrometry assay, therefore demonstrating this mechanism for the first time.
- Dong, Hai,Liu, Yu,Lv, Jian,Zhu, Jia-Jia
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p. 3307 - 3319
(2020/03/25)
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- Photoredox-Catalyzed Site-Selective α-C(sp3)?H Alkylation of Primary Amine Derivatives
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The synthetic utility of tertiary amines to oxidatively generate α-amino radicals is well established, however, primary amines remain challenging because of competitive side reactions. This report describes the site-selective α-functionalization of primary amine derivatives through the generation of α-amino radical intermediates. Employing visible-light photoredox catalysis, primary sulfonamides are coupled with electron-deficient alkenes to efficiently and mildly construct C?C bonds. Interestingly, a divergence between intermolecular hydrogen-atom transfer (HAT) catalysis and intramolecular [1,5] HAT was observed through precise manipulation of the protecting group. This dichotomy was leveraged to achieve excellent α/δ site-selectivity.
- Ashley, Melissa A.,Yamauchi, Chiaki,Chu, John C. K.,Otsuka, Shinya,Yorimitsu, Hideki,Rovis, Tomislav
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supporting information
p. 4002 - 4006
(2019/02/24)
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- Synthesis and in vitro investigation of potential antiproliferative monosaccharide–D-secoestrone bioconjugates
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The syntheses of monosaccharide–D-secoestrone conjugates are reported. They were prepared from 3-(prop-2-inyloxy)-D-secoestrone alcohol or oxime and monosaccharide azides via Cu(I)-catalyzed azide–alkyne cycloaddition reactions (CuAAC). The antiproliferat
- Bodnár, Brigitta,Mernyák, Erzsébet,Szabó, Johanna,W?lfling, János,Schneider, Gyula,Zupkó, István,Kupihár, Zoltán,Kovács, Lajos
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supporting information
p. 1938 - 1942
(2017/04/07)
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- Facile and Versatile Chemoenzymatic Synthesis of Enterobactin Analogues and Applications in Bacterial Detection
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Siderophores, such as enterobactin (Ent), are small molecules that can be selectively imported into bacteria along with iron by cognate transporters. Siderophore conjugates are thus a promising strategy for delivering functional reagents into bacteria. In this work, we present an easy-to-perform, one-pot chemoenzymatic synthesis of functionalized monoglucosylated enterobactin (MGE). When functionalized MGE is conjugated to a rhodamine fluorophore, which affords RhB-Glc-Ent, it can selectively label Gram-negative bacteria that utilize Ent, including some E. coli strains and P. aeruginosa. V. cholerae, a bacterium that utilizes linearized Ent, can also be weakly targeted. Moreover, the targeting is effective under iron-limiting but not iron-rich conditions. Our results suggest that the RhB-Glc-Ent probe is sensitive not only to the bacterial strain but also to the iron condition in the environment.
- Lee, Albert A.,Chen, Yi -Chen S.,Ekalestari, Elisa,Ho, Sheng -Yang,Hsu, Nai -Shu,Kuo, Tang -Feng,Wang, Tsung -Shing Andrew
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supporting information
p. 12338 - 12342
(2016/10/13)
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- New [(η5-C5H5)Ru(N-N)(PPh3)][PF6] compounds: Colon anticancer activity and GLUT-mediated cellular uptake of carbohydrate-appended complexes
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Eight ruthenium(ii) compounds of the general formula [(η5-C5H5)Ru(N-N)(PPh3)][PF6] were rationally designed, exhibiting high cytotoxicity against HCT116 human colon cancer cells, with IC50
- Florindo, Pedro R.,Pereira, Diane M.,Borralho, Pedro M.,Costa, Paulo J.,Piedade,Rodrigues, Cecília M. P.,Fernandes, Ana C.
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supporting information
p. 11926 - 11930
(2016/08/05)
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- AMYLOID TARGETING AGENTS AND METHODS OF USING THE SAME
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Provided herein is the design and synthesis of novel molecular rotor fluorophores useful for detection of amyloid or amyloid like proteins. The fluorophores are designed to exhibit enhanced fluorescence emission upon associating with amyloid or amyloid like proteins as compared to unbound compound. Also disclosed herein are the methods for treating of diseases associated with an amyloid or amyloid like proteins.
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Paragraph 00832
(2015/11/10)
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- Phosphatidylinositol 3-phosphate mimics based on a sulfoquinovose scaffold: Synthesis and evaluation as protein kinase B inhibitors
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New sulfoquinovose analogues of phosphatidylinositol 3-phosphate have been synthesised based on a sulfoquinovose scaffold as potential protein kinase B (PKB) inhibitors. The synthetic strategy involved the introduction into glucose of a thioacetate group at the 6-position and of an azide group at the anomeric position as precursors of the sulfonate and phosphoramidate moieties present in the final compounds. The synthesised compounds were tested in vitro on isolated PKB by means of ELISA assays and for their anti-proliferative activity against the human ovarian carcinoma cell line IGROV-1. Sulfoquinovose derivatives 2b and 2c showed inhibitory activity in the low micromolar range.
- Gabrielli, Luca,Calloni, Ilaria,Donvito, Giulia,Costa, Barbara,Arrighetti, Noemi,Perego, Paola,Colombo, Diego,Ronchetti, Fiamma,Nicotra, Francesco,Cipolla, Laura
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supporting information
p. 5962 - 5967
(2015/03/30)
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- Linear poly(amide triazole)s derived from d -glucose
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The click reaction between azides and alkynes is been increasingly employed in the preparation of polymers. In this article, we describe the synthesis and click polyaddition reaction of a new A-B-type amide monomer - prepared from d-glucose as renewable r
- Molina-Pinilla, Inmaculada,Bueno-Martinez, Manuel,Hakkou, Khalid,Galbis, Juan A.
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p. 629 - 638
(2014/02/14)
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- Diesterification of 3-[(β-cyclodextrinyl)succinamido]propane-1,2-diol catalysed by lipase: Diastereoselectivity or tridimensional substrate specificity?
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The transesterification of 3-[(β-cyclodextrinyl)succinamido]propane-1,2-diol with fatty esters catalyzed by immobilized lipase from Mucor miehei occurred with very different conversions of the two diastereoisomers [(R)- or (S)-amidopropanediol]. The highe
- Gervaise, Cédric,Bonnet, Véronique,Nolay, Florian,Cézard, Christine,Stasik, Imane,Sarazin, Catherine,Djeda?ni-Pilard, Florence
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p. 6200 - 6209
(2015/03/30)
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- Synthesis and glycosidase inhibitory profiles of functionalised morpholines and oxazepanes
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In this work libraries of morpholines and oxazepanes have been prepared via the reductive amination reaction between dialdehydes, derived from carbohydrates, and a range of amines. In this way, functionalised morpholines and oxazepanes have been prepared
- Burland, Peter A.,Osborn, Helen M.I.,Turkson, Andrea
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experimental part
p. 5679 - 5692
(2011/10/31)
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- Polycationic glycosides
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Cationic lipids have long been known to serve as antibacterial and antifungal agents. Prior efforts with attachment of cationic lipids to carbohydrate-based surfaces have suggested the possibility that carbohydrate-attached cationic lipids might serve as antibacterial and antifungal pharmaceutical agents. Toward the understanding of this possibility, we have synthesized several series of cationic lipids attached to a variety of glycosides with the intent of generating antimicrobial agents that would meet the requirement for serving as a pharmaceutical agent, specifically that the agent be effective at a very low concentration as well as being biodegradable within the organism being treated. The initial results of our approach to this goal are presented.
- Engel, Robert,Ghan, Ishrat,Montenegro, Diego,Thomas, Marie,Klaritch-Vrana, Barbara,Castano, Alejandra,Friedman, Laura,Leb, Jay,Rothman, Leah,Lee, Heidi,Capodiferro, Craig,Ambinder, Daniel,Cere, Eva,Awad, Christopher,Sheikh, Faiza,Rizzo Lee, Jaime,Nisbett, Lisa-Marie,Testani, Erika,Melkonian, Karin
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experimental part
p. 1508 - 1518
(2011/04/24)
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- Quantifying the electronic effects of carbohydrate hydroxy groups by using aminosugar models
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Methyl amino-deoxy-glycosides with α- and β-gluco, α-galacto, or α-manno stereochemistry with the amino functionality in each of the four possible non-anomeric positions have been synthesized and their pKa values determined by titration. These
- Pedersen, Christian M.,Olsen, Jacob,Brka, Azra B.,Bols, Mikael
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scheme or table
p. 7080 - 7086
(2011/07/08)
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- Synthesis and antibacterial activity of aminodeoxyglucose derivatives against Listeria innocua and Salmonella typhimurium
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In this study aminodeoxyglucose derivatives were synthesized and evaluated for their antibacterial activity against two food bacteria, Listeria innocua and Salmonella typhimurium. 6-Amino-6-deoxy-α-Dmethylglucopyranose (GSA-6), 3-amino-3-deoxy-D-glucopyranoside (GSA-3), and β-D-glucopyranosylamine (GSA-1) were synthesized and concurrently tested with commercially available D-glucosamine (GSA-2) for antibacterial activity. Results obtained from this study showed a pronounced antagonist effect due to the position of amino groups of aminoglucose derivatives on the antibacterial activity. GSA-3 was the most active compound. At a concentration of 2 × 10 -4 mol mL -1, it delayed the growth of both bacteria with percentages of inhibition of 29 and 15% for L. innocua and S. typhimurium, respectively. At the same concentration the percentages of inhibition for other aminodeoxyglucoses varied between 5 and 18% and between 2 and 11% for L. innocua and S. typhimurium, respectively. All compounds were characterized by FTIR, 1H NMR, and 13C NMR spectroscopy.
- Theoneste, Muhizi,Stephane, Greller,Veronique, Coma
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experimental part
p. 8770 - 8775
(2010/07/17)
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- Polycations. 17. Synthesis and properties of polycationic derivatives of carbohydrates
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In our continuing investigation of polycationic salts for purposes of antimicrobial action, ion-channel blocking, and construction of ionic liquids, we have prepared several series of polycationic salts derived from carbohydrate precursors. These salts are currently being investigated for optimal efficacy as antibacterials and antifungals, as well as for other applications. The syntheses of such series of salts are described here along with preliminary antibacterial testing results and a discussion of their properties indicating their potential utility for several purposes.
- Thomas, Marie,Montenegro, Diego,Castano, Alejandra,Friedman, Laura,Leb, Jay,Huang, Mia Lace,Rothman, Leah,Lee, Heidi,Capodiferro, Craig,Ambinder, Daniel,Cere, Eva,Galante, Jessica,Rizzo, JaimeLee,Melkonian, Karin,Engel, Robert
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experimental part
p. 1620 - 1627
(2009/12/24)
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- Development and characterization of lysine based tripeptide analogues as inhibitors of Sir2 activity
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Sirtuins are NAD+ dependent deacetylases that modulate various essential cellular functions. Development of peptide based inhibitors of Sir2s would prove useful both as pharmaceutical agents and as effectors by which downstream cellular alterations can be monitored. Click chemistry that utilizes Huisgen's 1,3-dipolar cycloaddition permits attachment of novel modifications onto the side chain of lysine. Herein, we report the synthesis of peptide analogues prepared using click reactions on Nε-propargyloxycarbonyl protected lysine residues and their characterization as inhibitors of Plasmodium falciparum Sir2 activity. The peptide based inhibitors exhibited parabolic competitive inhibition with respect to acetylated-peptide substrate and parabolic non-competitive inhibition with NAD+ supporting the formation of EI2 and E·NAD+·I2 complexes. Cross-competition inhibition analysis with the non-competitive inhibitor nicotinamide (NAM) ruled out the possibility of the NAM-binding site being the second inhibitor binding site, suggesting the presence of a unique alternate pocket accommodating the inhibitor. One of these compounds was also found to be a potent inhibitor of the intraerythrocytic growth of P. falciparum with 50% inhibitory concentration in the micromolar range.
- Chakrabarty, Subhra Prakash,Ramapanicker, Ramesh,Mishra, Roli,Chandrasekaran, Srinivasan,Balaram, Hemalatha
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scheme or table
p. 8060 - 8072
(2010/03/24)
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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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- New class of quaternary ammonium salts, derivatives of methyl D-glucopyranosides
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Reactions of two aromatic and two aliphatic amines with methyl 6-O-p-toluenesulfonyl-α-D-glucopyranoside or methyl 6-O-p-toluenesulfonyl- β-D-glucopyranoside were performed on a micro-scale. The synthesis and preparative isolation methods have been develo
- Pellowska-Januszek, Lucyna,Dmochowska, Barbara,Skorupa, Eugenia,Chojnacki, Jaroslaw,Wojnowski, Wieslaw,Wisniewski, Andrzej
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p. 1537 - 1544
(2007/10/03)
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- Analogues of moranoline and MDL 73945. Methyl 6(5)-deoxy-6(5)-(morpholin-4-yl)α-D-glycosides as glucosidase inhibitors
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Methyl 2,3,4-tri-O-acetyl-6-O-(p-tolylsulfonyl)-α-D-glucopyranoside (6), or its iodo analogue 7, were subjected to nucleophilic displacement with morpholine to give 8, deacetylation of which gave methyl 6-deoxy-6-(morpholin-4-yl)-α-D-glucopyranoside (3). Similarly, 11, 12 and 21 were prepared. The 6-deoxy-6-iodo derivative 16 was subjected to nucleophilic displacement with morpholine and subsequent acetylation to give 15. Deacetylation of 15 gave 17. The kinetic studies for the inhibition of β-D-glucosidase from sweet almond and using o-nitrophenyl β-D-glucopyranoside as substrate exhibited a Ki value for 21 on the same order as 1-deoxynojirimycin whereas for 3, a Ki value of lesser order was observed.
- El Ashry, El Sayed H.,Abdel-Rahman, Adel A.-H.,Kattab, Mohamed,Shobier, Aida H.,Schmidt, Richard R.
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p. 345 - 357
(2007/10/03)
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- Synthesis of Methyl 6-Deoxy-6-diphenylphosphino-α-D-glucopyranoside: Temperature-Dependence of the Primary O-Tosyl Cleavage Mode
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Methyl α-D-glucopyranoside is converted to methyl 6-p-toluenesulfonyl-2,3,4-tris-O-trimethylsilyl-α-D-glucopyranoside 2 and then reacted with lithium diphenylphosphide in THF. When the reaction is carried out at room temperature and below, S-O cleavage dominates giving methyl 2,3,4-tris-O-trimethylsilyl-α-D-glucopyranoside 3, whereas at 60°C in THF or at 35°C in diethyl ether, C-O cleavage occurs yielding the title carbohydrate-phosphine 4 in good yield after deprotection.
- Dahlhoff, Wilhelm V.,Radkowski, Karin
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p. 891 - 896
(2007/10/03)
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- Regioselective monotosylation of non-protected and partially protected glycosides by the dibutyltin oxide method
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Tosylation of non-protected glycopyranosides with p-toluenesulfonyl chloride in the presence of 4-dimethylaminopyridine, after activiation of the glycosides by dibutyltin oxide, gave mono-O-tosylates in good yield. The regioselectivity in this tosylation
- Tsuda,Nishimura,Kobayashi,Sato,Kanemitsu
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p. 2883 - 2887
(2007/10/02)
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- SELECTIVE DEOXYGENATION VIA REGIOSELECTIVE THIOACYLATION OF NON-PROTECTED GLYCOPYRANOSIDES BY THE DIBUTYLTIN OXIDE METHOD
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Regioselective thioacylation of some non-protected glycopyranosides ( Me α-D-Glc, Me β-D-Glc, Me α-D-Xyl, Me β-D-Xyl ) was examined by the dibutyltin oxide method, using phenoxythiocarbonyl chloride as the thioacylating agent.This method gave the mono-thionocarbonates regioselectively in high yields.Acetylation of these thionocarbonates followed by deoxygenation with tributyltin hydride smoothly gave the corresponding deoxy derivatives, except for the primary thionocarbonates.Similar treatment of the pyranosides that have a cis-vicinal glycol ( Me α-D-Gal, Me β-D-Gal, Me β-L-Ara, and Ph α-L-Ara ) led to the formation of cyclic thionocarbonates, which on acetylation followed by olefination with trimethyl phosphite afforded the unsaturated derivatives in satisfactory yields.On deacetylation and subsequent hydrogenation over platinic oxide, they gave the corresponding dideoxy derivatives quantitatively.The compounds thus prepared were identified by analyses of their proton and carbon-13 nuclear magnetic resonance spectra.Keywords - glycopyranoside; regioselective thioacylation; dibutyltin oxide; deoxygenation; cis-vicinal glycol; thionocarbonate; cyclic thionocarbonate; deoxy, dideoxy sugar; unsaturated sugar; 13C-NMR
- Haque, Ekramul Mohammed,Kikuchi, Tohru,Kanemitsu, Kimihiro,Tsuda, Yoshisuke
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p. 1016 - 1029
(2007/10/02)
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- The formation of branched-chain deoxypentofuranosides by ring contraction in the reductive desulfonyloxylation of hexopyranoside p-toluenesulfonates
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Several methyl 6-deoxy-, 6-deoxy-6-halo-, and 6-O-p-tolylsulfonylhexopyranoside 2- and 4-p-toluenesulfonates reacted readily with lithium triethylborohydride in boiling tetrahydrofuran under reductive desulfonyloxylation at C-2 and C-4, respectively, and
- Baer, Hans H.,Astles, David J.,Chin, Ho-chi,Siemsen, Lisa
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p. 432 - 439
(2007/10/02)
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- REGIOSELECTIVE STANNYLATION. ACYLATION OF CARBOHYDRATES: COORDINATION CONTROL
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An efficient method for the regioselective enhancement of the nucleophilicity of polyhydroxy compounds has been developed.Partial stannylation of carbohydrate with (Bu3Sn)2O and subsequent electrophilic attack with benzoyl chloride gave rise to regioselec
- Ogawa, Tomoya,Matsui, Masanao
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p. 2363 - 2370
(2007/10/02)
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