Anhydro Sugars Research Articles

1,6-anhydro-β- d-glucopyranose (β-glucosan), a constituent of human urine

When screening for abnormal urinary saccharides with one-dimensional thin-layer chromatography, an unknown component was observed in a position just above that of xylose. This compound was studied by gas chromatography-mass spectrometry and identified as the anhydro sugar β-glucosan. It was observed in approximately 20% of all urine samples investigated by thin-layer chromatography. Excretory levels varied widely from zero up to 5.3 mmol/l. No correlation with age or disease could be established. The compound was thought to be of exogenous origin.

ChemInform Abstract: Carbohydrate Chemistry. Ethers and Anhydro Sugars

Chemischer InformationsdienstVolume 17, Issue 29 Reviews ChemInform Abstract: Carbohydrate Chemistry. Ethers and Anhydro Sugars N. R. WILLIAMS, N. R. WILLIAMSSearch for more papers by this authorB. E. DAVISON, B. E. DAVISONSearch for more papers by this authorR. J. FERRIER, R. J. FERRIERSearch for more papers by this authorR. H. FURNEAUX, R. H. FURNEAUXSearch for more papers by this author N. R. WILLIAMS, N. R. WILLIAMSSearch for more papers by this authorB. E. DAVISON, B. E. DAVISONSearch for more papers by this authorR. J. FERRIER, R. J. FERRIERSearch for more papers by this authorR. H. FURNEAUX, R. H. FURNEAUXSearch for more papers by this author First published: July 22, 1986 https://doi.org/10.1002/chin.198629350Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume17, Issue29July 22, 1986 RelatedInformation

ChemInform Abstract: Branched‐Chain Sugars. Part 38. Ring‐Opening Reactions of Some Branched‐Chain Anhydro Sugars Using Hydride and Azide as Nucleophiles.

AbstractDie Öffnung des Oxiranringes verschiedener verzweigter Anhydrozucker wie (II) und (III) führt, abhängig vom′ verwendeten nucleophilen Reagens und von der Stereochemie der jeweiligen Ausgangsverbindung, zu diaxialen (II) und (IV) bzw. diäquatorialen Öffnungsprodukten (V).

ChemInform Abstract: Syntheses with Anhydro Sugars. Part 36. Reaction of 1,6‐Anhydro‐4‐O‐benzyl‐ 2‐deoxy‐2‐isothiocyanato‐β‐D‐glucopyranose.

AbstractDas aus dem Arninoderivat (Ia) sukzessiv über die Stufen (Ib)‐(Id) erhältliche Ureidoderivat (Ie) wird zum Tosylat (II) umgesetzt, dessen Cyclisierung das Thiazolin (III) liefert.

Ring-opening reactions of some branched-chain anhydro sugars using hydride and azide as nucleophiles

Ring-opening reactions of some branched-chain anhydro sugars using hydride and azide as nucleophiles

Antimicrobial effect of sugar osazones and anhydro sugars.

The antimicrobial effect of 14 sugar osazones and anhydro sugars was studied with model strains of Micrococcus luteus, Bacillus licheniformis, Escherichia coli and strains Staphylococcus aureus and Pseudomonas aeruginosa isolated from clinical material. The relationship between the structure of these compounds, their solubility in water and 1-octanol and antimicrobial effect was investigated.

Notizen: Epoxide Assisted Displacement of Triflyl Group by Fluoride Ion. An Efficient Approach to Fluorodeoxy Sugars

Abstract Displacement of triflyl group by fluoride ion in benzyl 2,3-anhydro sugars leads with stereochemical inversion to fluorodeoxy sugars, providing a general method for the introduction of fluorine in the neighbourhood of oxirane ring in anhydro sugars. This procedure is mild, convenient, and does not experience difficulties which sometime are encountered in nucleophilic fluoride displacements in carbohydrate systems.

Synthesis of fluorinated carbohydrates by the reaction of acetyl hypofluorite with glycals

Fluorinated carbohydrates have continued to attract much interest principally because of the use of [ 18F] 2-deoxy-2-fluoro- D -glucopyranose ([ 18F] 2FDG), a proven glucose analogue, as an imaging agent in studies of regional cerebral glucose metabolism by positron emission tomography (PET). Previous synthetic routes have included the electrophilic addition to tri- O -acetyl- D -glucal of trifluoromethyl hypofluorite (CF 3OF), of elemental fluorine or of xenon difluoride and fluoride displacement on an anhydro sugar. All of these methods have disadvantages, resulting in either low product yields, isomeric product mixtures and/or difluorinated compounds. These approaches have further disadvantages in the context of [ 18F]-radiolabelling in that, all of the above reagents, with the exception of F 2, are difficult to produce with 18F. While the use of [ 18F] F 2 has become routine in the production of [ 18F] 2FDG only about 10% of the 18F used is incorporated in the desired product. Prompted by the recent report of a simple preparation of acetyl hypofluorite (CH 3CO 2F) from F 2, we have investigated the reaction of this electrophilic fluorinating reagent with tri- O -acetyl-glucal, and also with the galacto analogue. In each case a high yield (78% and 84% respectively) of the 2-deoxy-2-fluoro products, corresponding to cis-addition of the hypofluorite to the sugar ring, has been isolated.

Conformational analysis of 1,2-anhydro-3,4,6-tri- O-benzyl-α- d-glucopyranose and -β- d-mannopyranose

The 1H- and 13C-n.m.r. spectra of 1,2-anhydro-3,4,6-tri- O-benzyl-α- d-glucopyranose and -β- d-mannopyranose were completely assigned by using single-frequency decoupling, off-resonance decoupling, and a spin-simulation program. The conformations of the two anhydro sugars were determined from their proton coupling-constants. The gluco isomer was found to be 4 H 5 (half-chair). The conformation of the manno derivative was found to be predominantly 4 H 5, with some ring flattening.

Graft copolymerization of anhydro sugar derivatives from macromolecular halides

AbstractCationic graft copolymerizations of bicyclic acetals, 1,6‐anhydro‐2,3,4‐tri‐O‐benzyl‐β‐D‐glucopyranose (LGTBE) and 1,6‐anhydro‐2,3,4‐tri‐O‐methyl‐β‐D‐glucopyranose (LGTME), were investigated with macromolecular carbenium ions formed from polymers that contain reactive halogens. Macromolecular complex catalysts formed from chlorosulfonated polyethylene or poly(isoprene‐co‐chloromethylstyrene) by the action of phosphorus pentafluoride yielded graft copolymers with low proportions (0.6–16%) of poly(LGTBE) or poly(LGTBE‐co‐epichlorohydrin) branchings. It was found that macromolecular complex catalysts formed from poly(styrene‐co‐fluoromethylstyrene) or poly(methyl methacrylate‐co‐fluoromethylstyrene) by the action of boron trifluoride etherate give graft copolymers with high proportions (up to 80%) of poly(LGTBE) or poly(LGTME) branchings. In addition, the model reactions for the graft copolymerization of LGTBE were examined with organic halide‐PF5, organic halide‐AgPF6, and organic fluoride‐BF3·OEt2 catalytic systems, of which the last two indicate that the polymerization is effected by a carbenium ion mechanism.

Synthesis of a substituted 2,6-dioxabicyclo[3.1.1]heptane,1,3-anhydro-2,4,6-tri- O-benzyl-β- d-glucopyranose

1,3-Anhydro-2,4,6-tri- O-benzyl-β- d-glucopyranose has been synthesized by ring closure of 2,4,6-tri- O-benzyl-α- d-glucopyranosyl chloride via two reaction sequences. The preferable method has allyl 3- O-allyl- d-glucopyranoside as key inter-mediate. This appears to be the first example of an anhydro sugar derivative with the 2,6-dioxabicyclo [3.1.1]heptane skeleton.

Synthesis of seven- and eight-carbon sugar derivatives from 2,3:5,6-di-O-isopropylidene-D-gulono-1,4-lactone and preparation of a new anhydro sugar

Synthesis of seven- and eight-carbon sugar derivatives from 2,3:5,6-di-O-isopropylidene-D-gulono-1,4-lactone and preparation of a new anhydro sugar

31P and 19F NMR spectroscopic studies on ring‐opening polymerization of 1,6‐anhydro‐2,3,4‐tri‐O‐benzyl‐β‐D‐glucopyranose by PF5 catalyst

AbstractIn order to elucidate the catalytic behavior of phosphorus pentafluoride in the polymerization of anhydro sugars, 13P and 19F NMR spectra were measured on a reaction mixture of 1,6‐anhydro‐2,3,4‐tri‐O‐benzyl‐β‐D‐glucopyranose (LGTBE) and PF5 with different mole ratios in a temperature range of −40 to −80°C. In the 31P NMR spectrum measured at low temperatures, there was a total of 16 peaks, which consisted of a broad quintet, a septet, and a sharp quartet, being assigned to the PF4O‐group, to PF, and to POF3, respectively. These fluoro compounds were also determined by the 19F NMR spectrum of the reaction mixture. The concentration of PF ions was found to correspond to that of oxonium ions, which are assumed to be actual propagating species, by determining both the concentration of PF from 19F NMR spectrum and the degree of polymerization of 2,3,4‐tri‐O‐benzyl‐α‐D‐glucopyranan obtained. Formation of the PF5: LGTBE complex was observed from the 31P NMR spectrum of the polymerization system at −80°C, which exhibits a broad sextet as well as absorptions due to POF3, PF4O–, and PF. To confirm the PF5:LGTBE complex, the NMR measurement of the PF5: tetrahydropyran complex was carried out. A polymerization mechanism of LGTBE by PF5 catalyst is discussed on the basis of the NMR measurement of the polymerization system.

Polymerization of anhydro sugar derivatives. Cationic polymerization of 5,6‐anhydro‐1,2‐O‐isopropylidene‐α‐D‐glucofuranose and structure of the polymer

AbstractThe cationic polymerization of 5,6‐anhydro‐1,2‐O‐isopropylidene‐α‐D‐glucofuranose (1), containing an oxirane ring, gave a polymer whose structure was found to be poly(5,6‐anhydro‐1,2‐O‐isopropylidene‐α‐D‐glucofuranose) (2). Polymerizations with phosphorus pentafluoride, boron trifluoride etherate, stannic chloride, or antimony pentachloride below 10°C for 0,04 to 240h gave yields of 51,7 to 97,5% of polymers with M̄n in the range of 1290 to 9500. Polymerization above 20°C produced insoluble gels. The specific rotations of the polymers changed with the polymerization conditions, being in the range of −31,6° to −15,0°. The mechanism of the epoxide polymerization of the 5,6‐anhydro sugar derivatives is discussed.

Synthèse et réactivite du méthyl-2- O-benzoyl-3-bromo-3,6-didésoxy-α- l-altropyranoside et du méthyl-2- O-benzoyl-3-bromo-3,6-didésoxy-4- O-méthyl-α- l-altropyranoside

Methyl 2- O-benzoyl-3-bromo-3,6-dideoxy-α- l-altropyranoside ( 4) and methyl 2- O-benzoy]-3-bromo-3,6-dideoxy-4- O-methyl-α- l-altropyranoside ( 5) have been prepared from methyl-α- l-rhamnopyranoside, respectively, in 2 and 3 steps. Reduction of 4 with lithium aluminium hydride followed by acid hydrolysis afforded the 3,6-dideoxy- l- arabino-bexose ( l-ascarylose). The anhydro sugars 8 and 9 have been used as intermediates in the stereoselective synthesis of 6-deoxy-3- O-methyl- l-altropyranose ( l-vallarose) and of 3-amino-3-degxy- l-altro sugars. Under azidolysis conditions, and according to the temperature, 5 gave unsaturated sugars such as 20 and the derived 26, or azido compounds such as 21 and 24, and the derived sugar methyl 2-amino-2,3,6-trideoxy-α- l- threo-hexopyranosid-4-ulose ( 25).

Stereoselective total synthesis of methyl α- d- and α- l-glucopyranosides

Methyl α- l- and α- d-glucopyranodsides have been synthesized from mehtyl ( R)- and ( S)-(2-furyl)glycolates ( 3), respectively. The key intermediates, methyl 6- O-benzyl-2,3-dideoxy- l(and d)-hex-2-enopyranosid-4-uloses ( 13), were obtained in the seven steps from the ester 3, without change of configuration of the asymmetric center, which became C-5 in the sugar molecule. Reduction of the ketone group at C-4 in the glycoside 13 with sodium borohydride afforded the corresponding methyl 6- O-benzyl-2,3-dideoxy- erythro-hex-2-enopyranosides ( 14). Epoxidation of the double bond in 14, followed by oxirane ring-opening in the anhydro sugar 16, and subsequent catalytic hydrogenolysis of the benzyl group led to the title compounds.

Copolymerization of anhydroglucose and anhydromannose derivatives: Structure, reactivity, and conformational analyses

AbstractPhosphorus pentafluoride‐catalyzed copolymerization of 1,6‐anhydro‐2,3,4‐tri‐O‐(p‐methylbenzyl)‐β‐D‐glucopyranose (TXGL, monomer G) and 1,6‐anhydro‐2,3,4‐tri‐O‐benzyl‐β‐D‐mannopyranose (TBMN, monomer M) appears to follow classical copolymerization theory. Reactivity ratios calculated by the procedure of Mayo and Lewis were rG = 0.90 ± 0.08, rM = 11.5 ± 0.80, from which sequence distributions were calculated. A conformational analysis of anhydro sugar polymerization is presented to explain differences in reactivity of monomers and their derived cations in polymerization and copolymerization. The polymers and copolymers were characterized by viscosity, 1H‐ and 13C‐NMR spectroscopy, optical rotation, and circular dichroism. The reaction gives stereoregular polymers as have other polymerizations and copolymerizations of this class.

Synthesis of linear stereoregular glucomannan heteropolysaccharides

AbstractA series of stereoregular α‐(1 → 6) linked glucomannans have been prepared by Lewis acid‐catalyzed copolymerization of anhydro sugar derivatives followed by debenzylation. The products have been characterized for mole fraction of the individual monomer, and sequence lengths have been calculated from copolymerization data. The viscosity, specific rotation, and 13C nmr spectra have been correlated with the structure of the various copolymers.

3'-de-o-methyl-2', 3'-anhydro-lankamycin, a new macrolide antibiotic from Streptomyces violaceoniger.

AbstractA further examination of the products from fermentation broths of Streptomyces violaceoniger has yielded small quantities of several lankamycin related antibiotics and metabolites. One of the antibiotics has been characterized as 3″‐de‐O‐methyl‐2″,3″‐anhydro‐lankamycin. The anhydro sugar of the new lankamycin, 3‐methyl‐4‐O‐acetyl‐2,3,6‐trideoxy‐α‐L‐threo‐hex‐2‐enepyranoside was also isolated as the ethyl glycoside from fermentation broths of the same organism.

ChemInform Abstract: SYNTHESES WITH ANHYDRO SUGARS PART 24, ISOMERIZATION OF 2‐AMINO‐1,6/3,4‐DIANHYDRO‐2‐DEOXY‐BETA‐D‐GALACTOPYRANOSE TO 1,6‐ANHYDRO‐2,3‐DIDEOXY‐2,3‐EPIMINO‐BETA‐D‐GULOPYRANOSE IN ALKALINE MEDIUM

Chemischer InformationsdienstVolume 6, Issue 40 Preparative Organic Chemistry ChemInform Abstract: SYNTHESES WITH ANHYDRO SUGARS PART 24, ISOMERIZATION OF 2-AMINO-1,6/3,4-DIANHYDRO-2-DEOXY-BETA-D-GALACTOPYRANOSE TO 1,6-ANHYDRO-2,3-DIDEOXY-2,3-EPIMINO-BETA-D-GULOPYRANOSE IN ALKALINE MEDIUM M. CERNY, M. CERNYSearch for more papers by this authorO. JULAKOVA, O. JULAKOVASearch for more papers by this authorJ. PACAK, J. PACAKSearch for more papers by this authorM. BUDESINSKY, M. BUDESINSKYSearch for more papers by this author M. CERNY, M. CERNYSearch for more papers by this authorO. JULAKOVA, O. JULAKOVASearch for more papers by this authorJ. PACAK, J. PACAKSearch for more papers by this authorM. BUDESINSKY, M. BUDESINSKYSearch for more papers by this author First published: October 7, 1975 https://doi.org/10.1002/chin.197540104AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume6, Issue40October 7, 1975 RelatedInformation