The structures of D-arabinose and D-glucose oximes

Finch, Paul; Merchant, Zohar M.

doi:10.1039/p19750001682

Cited by 41 publications

(22 citation statements)

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“…In accordance with previously reported spectroscopic data, [18b,23,25] for glucose conjugates of N-methylhydroxylamines, we found that the conjugates Bz(M-AE)-Glc and Ac(M-AMB)Glc were obtained in the 4 C 1 conformation with complete diastereoselectivity as β-pyranose forms. Also compound Boc(AMB)Glc, was in agreement with our prediction [28] as NMR spectroscopic analysis revealed the presence of both open-chain and ring-closed tautomers as follows: (E)-oxime/(Z)-oxime/β-pyranose ringchain in 60:20:20 ratio respectively. No structural characterization has been previously reported in the literature concerning conjugates between carbohydrates and N-benzylhydroxylamines.…”

Section: Resultssupporting

confidence: 89%

Chemoselective Reagents for Covalent Capture and Display of Glycans in Microarrays

2010

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Glycobiology has made very significant progress in the past decades. However, further progress will significantly depend on the establishment of novel methods for miniaturized, high‐throughput analysis of glycan–protein interactions. Robust solid‐phase chemical tools and new, chemoselective reagents for biologically meaningful display of surface‐immobilized glycans are likely to play a key role. Here we present four new bifunctional linkers that allow highly chemoselective capture of unprotected glycans in solution to form glycan‐linker conjugates for direct construction of glycan microarrays (glycochips). The bifunctional linkers carry O‐linked aminooxy moieties, some with N‐substituents at one end and an amino group at the other. In addition, they contain a substituted benzene ring for UV traceability and improved purification of glycan‐linker conjugates. NMR spectroscopic studies in solution proved that N‐substituted aminooxy linkers provided model glycan‐linker conjugates with the β‐glucopyranoside configuration, i.e. the ring‐closed form required for biological recognition. Then an ensemble of glycan‐linker conjugates were assembled from mannobiose, lactose, and N‐acetyl‐lactosamine and used for covalent printing of glycan microarrays. The stability of oximes were studied both in solution and on‐chip. In solution, two of the linkers provided glycan‐linker conjugates with a remarkable stability at pH 4 or higher, on‐chip this relative stability was upheld. Two of the linkers, with different properties, are recommended for the glycobiology toolbox for the construction of glycan microarrays from unprotected glycans.

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Section: Resultssupporting

confidence: 89%

Chemoselective Reagents for Covalent Capture and Display of Glycans in Microarrays

2010

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“…[8] Additionally, Nmethyl substituted aminooxy derivatives have been pursued. [9,28] Carbohydrate oximes and oxime ethers are known to exist in several ring-chain tautomeric forms, [29] of which the open-chain E and Z forms generally predominate over the pyranose b and a forms, [30][31][32] as shown for d-glucose in Scheme 1. Additionally, furanose b and a forms may constitute minor tautomers (not shown).…”

Section: Introductionmentioning

confidence: 98%

Chemoselective Capture of Glycans for Analysis on Gold Nanoparticles: Carbohydrate Oxime Tautomers Provide Functional Recognition by Proteins

Thygesen¹,

Sauer²,

Jensen³

2009

Chemistry A European J

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Nanoparticles functionalized with glycans are emerging as powerful solid-phase chemical tools for the study of protein-carbohydrate interactions using nanoscale properties for detection of binding events. Methods or reagents that enable the assembly of glyconanoparticles from unprotected glycans in two consecutive chemoselective steps with meaningful display of the glycan are highly desirable. Here, we describe a novel bifunctional reagent that 1) couples to glycans by oxime formation in solution, 2) aids in purification through a lipophilic trityl tag, and 3) after deprotection then couples to gold nanoparticles through a thiol. NMR studies revealed that these oximes exist as both the open-chain and N-glycosyl oxy-amine tautomers. Glycan-linker conjugates were coupled through displacement of ligands from preformed, citrate-stabilized gold nanoparticles. Recognition of these glycans by proteins was studied with a lectin, concanavalin A (ConA), in an aggregation assay and with a processing enzyme and glucoamylase (GA). We demonstrate that the presence of the N-glycosyl oxy-amines clearly enables functional recognition in sharp contrast to the corresponding reduced oxy-amines. This concept is then realized in a novel reagent, which should facilitate nanoglycobiology by enabling the operationally simple capture of glycans and their biologically meaningful display.

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“…An exception is glucose, from which the E-and Z-open-chain oximes 10 and 11 and the Nb-d-glucopyranosylhydroxylamine 12 have been prepared (Scheme 1). [34][35][36][37][38] Recently, the synthesis of a cyclic N-b-d-xylofuranosylhydroxylamine has been reported. [39] We prepared the crystalline compound 12 (yield 82 %) by stirring glucose with hydroxylamine in dry methanol at 20-25 8C.…”

Section: Resultsmentioning

confidence: 99%

Nitrosation of Sugar Oximes: Preparation of 2‐Glycosyl‐1‐hydroxydiazene‐2‐oxides

Brand¹,

Huhn²,

Groth³

et al. 2005

Chemistry A European J

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Oximes of glucose, xylose, lactose, fructose, and mannose have been prepared. Nitrosation of the oximes of glucose, xylose, and lactose with NaNO2/HCl afforded 2‐(β‐glycopyranosyl)‐1‐hydroxydiazene‐2‐oxides, which were isolated as salts 13, 22, and 28. Nitrosation of fructose oxime 29 furnished fructose, whereas nitrosation of mannose oxime 30 with NaNO2/HCl afforded the 1‐hydroxy‐2‐(β‐d‐mannopyranosyl)diazene‐2‐oxide 32, from which the p‐anisidinium salt 31 and the sodium salt 33 were prepared. However, nitrosation of 30 with isopentyl nitrite in aqueous solutions of CsOH or KOH resulted in the formation of the 2‐(α‐D‐mannofuranosyl)‐1‐hydroxydiazene‐2‐oxide salts 34 and 35, respectively. Methylation of the ammonium 2‐(β‐D‐glucopyranosyl)‐1‐hydroxydiazene‐2‐oxide 13 yielded the 1‐methoxy compound, which was benzoylated to afford the tetra‐O‐benzoate 14 a, the structure of which was confirmed by X‐ray diffraction analysis. From the glucose O‐methyloximes 15 and 16 the N‐methoxy‐N‐nitroso‐2,3,4,6‐tetra‐O‐acetyl‐β‐D‐glucopyranosylamine 18 was prepared. The structure of this compound was confirmed by X‐ray diffraction analysis. Treatment of acetobromoglucose with cupferron furnished the 1‐(2,3,4,6‐tetra‐O‐acetyl‐β‐D‐glucopyranosyloxy)‐2‐phenyldiazene‐2‐oxide 20.

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The structures of D-arabinose and D-glucose oximes

Abstract: marabinose oxirne, m.p. 156-137*, which consist of a mixture of SYS-(80%) a d uMS-(20%) forms.

Cited by 41 publications

References 0 publications

Chemoselective Reagents for Covalent Capture and Display of Glycans in Microarrays

Chemoselective Reagents for Covalent Capture and Display of Glycans in Microarrays

Chemoselective Capture of Glycans for Analysis on Gold Nanoparticles: Carbohydrate Oxime Tautomers Provide Functional Recognition by Proteins

Nitrosation of Sugar Oximes: Preparation of 2‐Glycosyl‐1‐hydroxydiazene‐2‐oxides

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