Chemo- and stereoselective glycosylation of hydroxylamino derivatives: A versatile approach to glycoconjugates

Peri, Francesco; Dumy, Pascal; Mutter, Manfred

doi:10.1016/s0040-4020(98)00763-7

Cited by 157 publications

(169 citation statements)

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“…The mechanism that we propose for the coupling reaction consists of the formation of an intermediate oxyiminium ion by reaction of the N,O-disubstituted hydroxylamine group with the aldehyde of the open-chain sugar (Scheme 2). [18] Monosaccharide 13, which has a methoxyamino group at C-6, was prepared according to the synthetic route depicted in Scheme 3.…”

Section: Resultsmentioning

confidence: 99%

“…[16] It is well known that when using a reacting unit bearing a ™primary∫ À O À NH 2 group, an open-chain sugar oxime is obtained, [17] but it has also been observed that the cyclic form of the sugar is restored when a peptide with a ™secondary∫ hydroxylamino group (RÀOÀNHÀR') is used. [18] By following this last approach, if R and R' were sugar units, it would be possible in principle to obtain disaccharides and, more generally, oligosaccharide mimics by working in water and avoiding the use of any activation and protection strategy. These mimics, however, differ from the natural product by the fact that two atoms ( À O À N À ) substitute the interglycosidic oxygen atom and they are therefore ™non-isosteric∫ analogues.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and Conformational Analysis of Novel N(OCH₃)‐linked Disaccharide Analogues

Peri

Jiménez‐Barbero

Garcı́a-Aparicio

et al. 2004

Chemistry A European J

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N(OMe)-linked disaccharide analogues, isosteric to the corresponding natural disaccharides, have been synthesized by chemoselective assembly of unprotected natural monosaccharides with methyl 6-deoxy-6-methoxyamino-alpha-D-glucopyranoside in an aqueous environment. The coupling reactions were found to be chemo- and stereoselective affording beta-(1-->6) disaccharide mimics when using Glc and GlcNAc; in the case of Gal, the beta-anomer was prevalent (beta:alpha=7:1). An iterative method for the synthesis of linear N(OMe) oligosaccharide analogues was demonstrated, based on the use of an unprotected monosaccharide building block in which an oxime functionality at C-6 is converted during the synthesis into the corresponding methoxyamino group. The conformational analysis of these compounds was carried out by using NMR spectroscopy, ab initio, molecular mechanics, and molecular dynamics methods. Optimized geometries and energies of fourteen conformers for each compound have been calculated at the B3LYP/6-31G* level. Predicted conformational equilibria were compared with the results based on NMR experiments and good agreement was found. It appears that N(OMe)-linked disaccharide analogues exhibit a slightly different conformational behavior to their parent natural disaccharides.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis and Conformational Analysis of Novel N(OCH₃)‐linked Disaccharide Analogues

Peri

Jiménez‐Barbero

Garcı́a-Aparicio

et al. 2004

Chemistry A European J

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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: 99%

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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“…1B). Although the stability of these model neoglycosides was not examined, the distribution of pyranose, and occasionally furanose, anomers in neoglycosides was found to be dependant on the identity of the sugar (15), and equilibration between the product isomers was sometimes observed (J.M.L. and J.S.T., unpublished data).…”

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confidence: 99%

Enhancing the anticancer properties of cardiac glycosides by neoglycorandomization

Langenhan¹,

Peters²,

Guzei³

et al. 2005

Proc. Natl. Acad. Sci. U.S.A.

216

174

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Glycosylated natural products are reliable platforms for the development of many front-line drugs, yet our understanding of the relationship between attached sugars and biological activity is limited by the availability of convenient glycosylation methods. When a universal chemical glycosylation method that employs reducing sugars and requires no protection or activation is used, the glycorandomization of digitoxin leads to analogs that display significantly enhanced potency and tumor specificity and suggests a divergent mechanistic relationship between cardiac glycosideinduced cytotoxicity and Na ؉ ͞K ؉ -ATPase inhibition. This report highlights the remarkable advantages of glycorandomization as a powerful tool in glycobiology and drug discovery.carbohydrate ͉ natural product ͉ sugar

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Chemo- and stereoselective glycosylation of hydroxylamino derivatives: A versatile approach to glycoconjugates

Cited by 157 publications

References 24 publications

Synthesis and Conformational Analysis of Novel N(OCH₃)‐linked Disaccharide Analogues

Synthesis and Conformational Analysis of Novel N(OCH₃)‐linked Disaccharide Analogues

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

Enhancing the anticancer properties of cardiac glycosides by neoglycorandomization

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Chemo- and stereoselective glycosylation of hydroxylamino derivatives: A versatile approach to glycoconjugates

Cited by 157 publications

References 24 publications

Synthesis and Conformational Analysis of Novel N(OCH3)‐linked Disaccharide Analogues

Synthesis and Conformational Analysis of Novel N(OCH3)‐linked Disaccharide Analogues

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

Enhancing the anticancer properties of cardiac glycosides by neoglycorandomization

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Synthesis and Conformational Analysis of Novel N(OCH₃)‐linked Disaccharide Analogues

Synthesis and Conformational Analysis of Novel N(OCH₃)‐linked Disaccharide Analogues