- Macrocyclic derivatives with a sucrose scaffold: insertion of a long polyhydroxylated linker between the terminal 6,6′-positions
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A series of five new macrocyclic hybrids with a sucrose scaffold were prepared by the reaction of activated 1′,2,3,3′,4,4′-hexa-O-methylsucrose with diversely functionalized d-mannitols. The 21-, 25-, and 31-membered representatives containing mannitol units were prepared by a macrocyclization of 6,6′-di-O-propargylated sucrose with protected 1,6-diazido-d-mannitol or 6,6′-di-azidosucrose with propargylated d-mannitol (a “click” approach), whereas 23-membered representatives were prepared by double N-alkylation of 1′,2,3,3′,4,4′-hexa-O-methyl-6,6′-di-aminosucrose with 1,6-di-bromoacyl d-mannitol. All sucrose derivatives were tested as putative hosts for chiral recognition of α-phenylethylammonium (α-PEA) cations. In one case, in striking contrast to all sucrose-based macrocyclic hosts previously reported by us, unexpected reverse preference for the R-enantiomer was observed (KR/KS = 1.5).
- Chaciak, Bartosz,D?browa, Kajetan,Swider, Pawe?,Jarosz, S?awomir
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- Aqueous Glycosylation of Unprotected Sucrose Employing Glycosyl Fluorides in the Presence of Calcium Ion and Trimethylamine
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We report a synthetic glycosylation reaction between sucrosyl acceptors and glycosyl fluoride donors to yield the derived trisaccharides. This reaction proceeds at room temperature in an aqueous solvent mixture. Calcium salts and a tertiary amine base promote the reaction with high site-selectivity for either the 3′-position or 1′-position of the fructofuranoside unit. Because nonenzymatic aqueous oligosaccharide syntheses are underdeveloped, mechanistic studies were carried out in order to identify the origin of the selectivity, which we hypothesized was related to the structure of the hydroxyl group array in sucrose. The solution conformation of various monodeoxysucrose analogs revealed the co-operative nature of the hydroxyl groups in mediating both this aqueous glycosyl bond-forming reaction and the site-selectivity at the same time.
- Pelletier, Guillaume,Zwicker, Aaron,Allen, C. Liana,Schepartz, Alanna,Miller, Scott J.
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p. 3175 - 3182
(2016/03/19)
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- CuAAC-mediated diversification of aminoglycoside-arginine conjugate mimics by non-reducing di- and trisaccharides
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Di- and triguanidinylation of trehalose, sucrose, and melizitose has been achieved via a Huisgen-cycloaddition approach. They can serve as aminoglycoside-arginine conjugate mimics, which has been demonstrated by their biological profiles in assays against
- Westermann, Bernhard,D?rner, Simon,Brauch, Sebastian,Schaks, Angela,Heinke, Ramona,Stark, Sebastian,Van Delft, Floris L.,Van Berkel, Sander S.
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- Efficient microwave assisted synthesis of novel 1,2,3-triazole-sucrose derivatives by cycloaddition reaction of sucrose azides and terminal alkynes
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Novel 1-(1′,2,3,3′,4,4′,6-hepta-O-acetyl-6′-deoxy- sucros-60-yl)-4-substituted-1,2,3-triazoles were synthesized by microwave assisted copper catalyzed 1,3-dipolar cycloaddition of sucrose derived azides with terminal alkynes in excellent yields and in sho
- Potewar, Taterao M.,Petrova, Krasimira T.,Teresa Barros
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- Library of mild and economic protocols for the selective derivatization of sucrose under microwave irradiation
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The chemistry of sucrose is very challenging due to its eight hydroxyl groups, three of which are primary, with very similar reactivities, thus control of the chemoselectivity is a central issue. In this work, the selective formation of monounsaturated es
- Barros, M. Teresa,Petrova, Krasimira T.,Correia-Da-Silva, Paula,Potewar, Taterao M.
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p. 1897 - 1906
(2011/09/19)
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- Direct azidation of unprotected carbohydrates under Mitsunobu conditions using hydrazoic acid
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A single step procedure for the direct and regioselective synthesis of carbohydrate azides from unprotected sugars using hydrazoic acid under Mitsunobu conditions is reported. A series of mono-, di-, or triazido polyhydroxylated systems are described.
- Besset, Céline,Chambert, Stéphane,Fenet, Bernard,Queneau, Yves
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experimental part
p. 7043 - 7047
(2010/02/28)
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- Isothiocyanates and cyclic thiocarbamates of α,α'-trehalose, sucrose, and cyclomaltooligosaccharides
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6,6'-dideoxy-6,6'-diisothiocyanato-α,α'-trehalose (4), 6-deoxy-6-isothiocyanato-α-D-fructofuranose β-D-fructopyranose 1,2':2,1'-dianhydride (11), 6,6'-dideoxy-6,6'-diisothiocyanatosucrose (16), and per(6-deoxy-6-isothiocyanato)-cyclomaltohexaose (23), -cyclomaltoheptaose (27), and -cyclomaltooctaose (31) have been prepared in high yield by reaction of the corresponding amino sugars with thiophosgene.In the absence of base, all isothiocyanates were stable and could be stored and acetylated without decomposition.In the presence of trietylamine, 6,6'-dideoxy-6,6'-diisothiocyanato-α,α'-trehalose underwent intramolecular cyclisation involving HO-4 to give the corresponding bis(cyclic thiocarbamate).The product of cyclisation at a single glucopyranosyl unit was obtained in the treatment of the above diisothiocyanate with mixed (H+, HO-) ion-exchange resin.Under identical reaction conditions, 6,6'-dideoxy-6,6'-diisothiocyanatosucrose yielded exclusively the product of intramolecular cyclisation at the D-glucopyranosyl moiety, while derivatives of α-D-fructofuranose β-D-fructopyranose 1,2':2,1'-dianhydride and cyclomaltooligosaccharides remained unchanged. Keywords: Sugar isothiocyanates; Trehalose; Difructose dianhydrides; Sucrose; Cyclomaltooligosaccharides
- Fernandez, Jose Manuel Garcia,Mellet, Carmen Ortiz,Blanco, Jose Luis Jimenez,Mota, Jose Fuentes,Gadelle, Andree,et al.
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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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- Transformation of Sucrose: An Alternative Route for Amination
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Mesylation of sucrose with 1 and 2 moles of mesylchloride (methane sulfonyl chloride) separately followed by acetylation in pyridine formed mono-, di-, tri- and tetra-O-mesyl sucrose-acetates respectively.Mono and dimesyl sucrose-acetates are converted into their amino derivatives via iodo and azido compounds in appreciable yields.
- Sharma, N. K.,Norula, J. L.,Mattey, S. K.
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p. 385 - 388
(2007/10/02)
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