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1.
Wolfgang A.R. van Heeswijk Fred R. Wassenburg Johannes F.G. Vliegenthart 《Carbohydrate research》1978,62(2):281-287
Reaction of 1,2-O-cyclopentylidene-α-d-glucofuranurono-6,3-lactone (2) with 2,3,4,6-tetra-O-acetyl-α-d-glucopyranosyl bromide (1) gave 1,2-O-cyclopentylidene- 5-O-(2,3,4,6-tetra-O-acetyl-α-d-glucopyranosyl)-α-d-glucofuranurono-6,3-lactone (3, 45%) and 1,2-O-cyclopentylidene-5-O-(2,3,4,6-tetra-O-acetyl-β-d-glucopyranosyl)-α-d-glucofuranurono-6,3-lactone (4, 38%). Reduction of 3 and 4 with lithium aluminium hydride, followed by removal of the cyclopentylidene group, afforded 5-O-α-(9) and -β-d-glucopyranosyl-d-glucofuranose (12), respectively. Base-catalysed isomerization of 9 yielded crystalline 5-O-α-d-glucopyranosyl-d-fructopyranose (leucrose, 53%). 相似文献
2.
3.
The effect of phenols on the hydrolysis of substituted phenyl β-d-gluco- and β-d-xylo-pyranosides by β-d-glucosidase from Stachybotrys atra has been investigated. Depending on the glycon part of the substrate and on the phenol substituent, the hydrolysis is either inhibited or activated. With aryl β-d-xylopyranosides, transfer of the xylosyl residue to the phenol, with the formation of new phenyl β-d-xylopyranosides, is observed. With aryl β-d-glucopyranosides, such transfer does not occur when phenols are used as acceptors, but it does occur with anilines. A two-step mechanism, in which the first step is partially reversible, is proposed to explain these observations. A qualitative analysis of the various factors determining the overall effect of the phenol is given. 相似文献
4.
Maltitol, crystallised from aqueous solution, has m.p. 146.5–147°, [α]d + 106.5° (water), and is orthorhombic with the space group P212121 and Z = 4, and with cell dimensions a = 8.166(5), b = 12.721(9), and c = 13.629(6) Å. The molecule shows a fully extended conformation with no intramolecular hydrogen-bonds. All nine hydroxyl groups are involved in intermolecular hydrogen-bond networks and in bifurcated, finite chains. The d-glucopyranosyl moiety has the 4C1 conformation, and the conformation about the C-5–C-6 bond is gauche-gauche. The d-glucitol residue has the bent [ap, Psc, Psc (APP)] conformation. The empirical formula for the solubility in water is C = 119.1 + 1.204 T + 4.137 × 10?2 T2 ? 7.137 × 10?4 T3 + 7.978 × 10?6 T4. The thermal properties are as follows: ΔHf = 13.5 kcal.mol?1, and Q = ?5.57 kcal.mol?1. 相似文献
5.
Methyl α-d-mannopyranoside (1 mole) reacts with 2,2-dimethoxypropane (1 mole), to give the 4,6-O-isopropylidene derivative (2) which rearranges to the 2,3-O-isopropylidene derivative (4). Compound4 can also be prepared by graded hydrolysis of methyl 2,3:4,6-di-O-isopropylidene-α-d-mannopyranoside. Successive benzoylation, oxidation, and reduction of4 provides a useful route to a number ofd-talopyranoside compounds. Methyl α-d-mannofuranoside (1 mole) reacts with 1–2 moles of 2,2-dimethoxypropane to give the 5,6-O-isopropylidene derivative (16) in 90% yield. 相似文献
6.
The intestinal transport of three actively transported sugars has been studied in order to determine mechanistic features that, (a) can be attributed to stereospecific affinity and (b) are common.The apparent affinity constants at the brush-border indicate that sugars are selected in the order, glucose, (the Km values are 1.23, 5.0 and 18.1 mM, respectively.) At low substrate concentrations the Kt values for Na+ activation of sugar entry across the brush-border are: 27.25, and 140 mequiv. for β-methyl glucose, galactose and 3-O-methyl glucose, respectively. These kinetic parameters suggest that Na+, water, sugar and membrane-binding groups are all factors which determine selective affinity.In spite of these differences in operational affinity, all three sugars show a reciprocal change in brush-border entry and exit permeability as Ringer [Na] or [sugar] is increased. Estimates of the changes in convective velocity and in the diffusive velocity when the sugar concentration in the Ringer is raised reveal that with all three sugars, the fractional reduction in convective velocity is approximately equal to the (reduction of diffusive velocity)2. This is consistent with the view that the sugars move via pores in the brush-border by convective diffusion.Theophylline reduces the serosal border permeability to β-methyl glucose and to 3-O-methyl glucose relatively by the same extent and consequently, increases the intracellular accumulation of these sugars.The permeability of the serosal border to β-methyl glucose entry is lower than permeability of the serosal border to β-methyl glucose exit, which suggests that β-methyl glucose may be convected out of the cell across the lateral serosal border. 相似文献
7.
Vitali I. Betaneli Michael V. Ovchinnikov Leon V. Bachinowsky Nikolay K. Kochetkov 《Carbohydrate research》1980,84(2):211-224
The koenigs-Knorr glycosylation of 4,6-O-ethylidene-1,2-O-isopropylidene-3-O-(2,3-O-isopropylidene-α-l-rhamnopyranosyl)-α-d-galactopyranose (3) by 4,6-di-O-acetyl-2,3-O-carbonyl-α-d-mannopyranosyl bromide (10), as well as Helferich glycosylations of 3 by tetra-O-acetyl-α-d-mannopyranosyl and -α-d-glucopyranosyl bromides, proceeded smoothly to give high yields of trisaccharide derivatives (12, 16, and 17). An efficient procedure for the transformation of 12, 16, and 17 into the α-deca-acetates of the respective trisaccharides has been developed. Zemplén de-acetylation then afforded the title trisaccharides in yields of 53, 52, and 62 %, respectively, from 3. A new route to 1,4,6-tri-O-acetyl-2,3-O-carbonyl-α-d-mannopyranose is suggested. 相似文献
8.
2-Deoxy-β-d-lyxo-hexose (2-deoxy-β-d-galactose, C6H12O5), Mr = 164.16, is monoclinic, P21 with a = 9.811(1), b = 6.953(1), c = 5.315(1) Å, β = 91.58(2)°, V = 362.5(1) Å3, Z = 2, and Dx = 1.504 g.cm?3. The structure was solved by direct methods (MULTAN 79) and refined to R = 0.032 for 800 observed reflections. Each hydroxyl oxygen, acting both as donor and acceptor, is involved in a hydrogen-bonding system, which consists of infinite helical chains around the crystallographic screw axes. Moreover, weak interactions allow the incorporation of the ring-oxygen atoms into an interconnected network. 相似文献
9.
Michael W. Winkley 《Carbohydrate research》1973,31(2):245-254
Reaction of 2,3,5-tri-O-benzyl-d-ribofuranosyl bromide with mercuric cyanide afforded an anomeric mixture of cyanides (3) and 1,4-anhydro-2,3,5-tri-O-benzyl-d-erythro-pent-1-enitol (6). Reduction of 3 with lithium aluminum hydride gave a pair of epimeric amines (4 and 5), which were separated by chromatography and characterized by conversion into the known 2,5-anhydro-3,4,6-tri-O-benzyl-1-deoxy-1-ureido-d-allitol (7) and its epimer, 2,5-anhydro-3,4,6-tri-O-benzyl-1-deoxy-1-ureido-d-altritol (8). Compound 8 and its precursor were used for the synthesis of various “α-homonucleosides”. 相似文献
10.
The rate constants for the hydrolysis of six alkyl and four aryl β-d-xylofuranosides in aqueous perchloric acid at various temperatures have been measured. The effects of varying the aglycon structure on the hydrolysis rate are interpreted in terms of two concurrent reactions. Either, the substrate, protonated on the glycosidic oxygen atom, undergoes a rate-limiting heterolysis to form a cyclic oxocarbonium ion, or, an initial rapid protonation of the ring oxygen is followed by a unimolecular cleavage of the five-membered ring, all subsequent reactions being fast. It is suggested that xylofuranosides having strongly electron-attracting aglycon groups react mainly by the former pathway, whereas the latter is more favourable for substrates having electron-repelling aglycon groups. The negative entropies of activation obtained with the latter compounds are attributed to the rate-limiting opening of the five-membered ring. The rate variations of the hydrolyses of alkyl β-d-xylofuranosides in aqueous perchloric acid-methyl sulfoxide mixtures are interpreted as lending further support for the suggested chance in mechanism. 相似文献
11.
Methods for the synthesis of 3-O-(α-d-mannopyranosyl)-d-mannose and 2-(4-aminophenyl)ethyl 3-O-(α-d-mannopyranosyl)-α-d-mannopyranoside have been investigated by a number of sequences. Glycosidations with 2,3-di-O-acetyl-4,6-di-O-benzyl-d-mannopyranosyl and 2-O-benzoyl-3,4,6-tri-O-benzyl-d-mannopyranosyl p-toluenesulfonates were found to give better yields than the Helferich modification, the use of a peracylated d-mannopyranosyl halide, or the use of triflyl leaving group. Only the α anomer was obtained. Factors influencing glycosidation reactions are discussed. A mercury(II) complex was used for selective 2-O-acylation of 4,6-di-O-benzyl-α-d-mannopyranosides. A disaccharide—protein conjugate was prepared by the isothiocyanate method. 相似文献
12.
3- O-(2-Acetamido-2-deoxy-β-d-glucopyranosyl)-α-d-galactopyranose (10, “Lacto-N-biose II”) was synthesized by treatment of benzyl 6-O-allyl-2,4-di-O-benzyl-β-d-galactopyranoside with 2-methyl-(3,4,6-tri-O-acetyl-1,2-dideoxy-α-d-glucopyrano)[2,1-d]-2-oxazoline (5), followed by selective O-deallylation, O-deacetylation, and catalytic hydrogenolysis. Condensation of 5 with benzyl 6-O-allyl-2-O-benzyl-α-d-galactopyranoside, followed by removal of the protecting groups, gave 10 and a new, branched trisaccharide, 3,4-di-O-(2-acetamido-2-deoxy-β-d-glucopyranosyl)-d-galactopyranose (27). 相似文献
13.
Treatment of methyl 2,3-anhydro-5-deoxy-α-d-ribofuranoside with lithium dimethyl cuprate gave methyl 2,5-dideoxy-2-C-methyl-α-d-arabinofuranoside (54% yield) and methyl 3,5-dideoxy-3-C-methyl-α-d-xylofuranoside (10%). The former was converted into its 3-O-acetyl and 3-O-benzyl derivatives, which, upon acid hydrolysis, afforded 3-O-acetyl- and 3-O-benzyl-2,5-dideoxy-2-C-methyl-d-arabinofuranose in 60–75% overall yield. Treatment of the 3-O-benzyl compound with ethanethiol in the presence of trifluoromethanesulfonic acid afforded 3-O-benzyl-2,5-dideoxy-2-C-methyl-d-arabinose diethyl dithioacetal (20%) and ethyl 3-O-benzyl-2,5-dideoxy-2-C-methyl-1-thio-α-d-arabinoside (73%). The former, which was also available from the latter by equilibration in acidic ethanethiol, was acetylated at O-4 and the product converted into the corresponding dimethyl acetal (85% overall yield). This compound was, after debenzylation, hydrolyzed with acid, to provide 4-O-acetyl-2,5-dideoxy-2-C-methyl-d-arabinose in 70% overall yield. 相似文献
14.
The Halide ion-catalysed reaction of benzyl exo-2,3-O-benzylidene-α-l-rhamnopyranoside with tetra-O-benzyl-α-d-galactopyranosyl bromide and hydrogenolysis of the exo-benzylidene group of the product 2 gave benzyl 3-O-benzyl-4-O-(2,3,4,6-tetra-O-benzyl-α-d-galactopyranosyl)-α-l-rhamnopyranoside (6). Compound 2 was converted into 4-O-α-d-galactopyranosyl-l-rhamnose. The reaction of 6 with tetra-O-acetyl-α-d-glucopyranosyl bromide and removal of the protecting groups from the product gave 4-O-α-d-galactopyranosyl-2-O-β-d-glucopyranosyl-l-rhamnose. 相似文献
15.
John H. Pazur Yoshio Tominaga Charles W. DeBrosse Lloyd M. Jackman 《Carbohydrate research》1978,61(1):279-290
The formation of 1,6-anhydro-β-d-glucopyranose and several d-glucosyl oligosaccharides has been observed during the action of a purified, fungal glucosyltransferase (EC 2.4.1.24) on maltose. Such products are synthesized by a transglucosylation mechanism involving the formation of a d-glucosyl-enzyme complex and the displacement of the d-glucosyl group by appropriate acceptor-substrates. The formation of the 1,6-anhydro bond is a novel type of transfer reaction and occurs by displacement of the enzyme from the d-glucosyl-enzyme complex by the proton of the primary hydroxyl group of the same glucosyl group. This reaction is characterized by inversion of configuration at the position of glucosidic bond-cleavage of the substrate. Synthesis of the d-glucosyl oligosaccharides occurs by displacement of the d-glucosyl groups from the enzyme by suitable acceptor-substrates. In these cases, the reactions are characterized by retention of configuration of the d-glucosidic bonds of the substrate. The list of oligosaccharides produced from maltose includes nigerose, kojibiose, isomaltose, maltotriose, panose, isomaltotriose, and 6-O-d-glucosyl-panose. The identity of these compounds has been established by methylation analysis and enzymic hydrolysis. d-Glucose is also a product of the reaction and arises from both the reducing and the non-reducing groups of maltose. 相似文献
16.
The synthesis of the title disaccharide derivative (1C), corresponding to the Salmonella O-factor 21, is described. Treatment of 2-O-benzyl-4-O-p-nitrobenzoyl-α-paratosyl bromide (5) with p-nitrophenyl 2-O-benzyl-4,6-O-benzylidene-α-d-mannoside in dichloromethane, in the presence of mercuric cyanide, gave the α- and β-linked disaccharide derivatives (6a and 6b) in yields of 34 and 5%, respectively. The disaccharide derivative 10 can react with free amino groups in proteins to produce artificial antigens useful in studies on Salmonella immunology. 相似文献
17.
Hydrolysis of purin-6-yl 2-deoxy-1-thio-β-d-arabino-hexopyranoside (2) to 6-mercaptopurine and 2-deoxy-d-glucose is catalyzed by hydronium ion and almond β-d-glucosidase. The dependence of rate on acidity in water and deuterium oxide indicates that 2 and its conjugate acid undergo hydrolysis via a mechanism that involves a partially rate-limiting proton transfer. Although 2 is ≈103 more reactive than 6-purinyl β-d-glucothiopyranoside (1) in dilute aqueous acid, 1 is a better substrate for almond β-d-glucosidase. 相似文献
18.
Elisabeth Besson Jean Chopin Kenneth R. Markham Rudiger Mues Herbert Wong Marie-Louise Bouillant 《Phytochemistry》1984,23(1):159-161
The structure of neoschaftoside is shown for the first time to be 6-C-β-d-glucopyranosyl-8-C-β-l-arabinopyranosylapigenin. A variety of chemical and spectroscopic techniques are involved. 相似文献
19.
7-Acetamido-6,7,8-trideoxy-1,2:3,4-di-O-isopropylidene-α-d- and -β-l-glycero-d-galacto-octopyranoses (8) and (9), intermediates for the synthesis of analogs of the antibiotic lincomycin, have been synthesized from cis-6,7,8-trideoxy-1,2:3,4-di-O-isopropylidine-7-C-nitro-α-d-galacto-oct-6-enose (4). The configuration of C-7 in compound 8 was determined by X-ray crystallagraphy. The crystals are orthorhombic, space group P21,2121 with Z4, in a unit cell of dimensions a2.457(1) nm, b1.380(1) nm, and c526(1) pm. The conformation of compound 8 in the solid state is °S2, slightly distorted towards °H5. 相似文献
20.
Shigehiro Kamitori Atsushi Ueda Yasuhiro Tahara Hiromi Yoshida Tomohiko Ishii Jun’ichi Uenishi 《Carbohydrate research》2011,(9):1182
The crystal structures of α-d-glucopyranosyl β-d-psicofuranoside and α-d-galactopyranosyl β-d-psicofuranoside were determined by a single-crystal X-ray diffraction analysis, refined to R1 = 0.0307 and 0.0438, respectively. Both disaccharides have a similar molecular structure, in which psicofuranose rings adopt an intermediate form between 4E and 4T3. Unique molecular packing of the disaccharides was found in crystals, with the molecules forming a layered structure stacked along the y-axis. 相似文献