Synthesis of S-linked thiooligosaccharide analogues of Nod factors. Part 1: selectively N-protected 4-thiochitobiose precursors

Auzanneau, France‐Isabelle; Bennis, Khalil; Fanton, Elisabeth; Promé, Danièlle; Defaye, J.; Gelas, Jacques

doi:10.1039/a802932f

Cited by 17 publications

(18 citation statements)

References 11 publications

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“…On the other hand, when GlcASH (5) was used, the reaction required 2.4 equivalents of base and HMPA as co-solvent, giving 45% yield of 10 (Table 1, entry 5). Similarly, H-3 appeared as a triplet at 3.02 ppm (J2,3  J3,4 = 10.7 Hz) in the 1 H-NMR spectrum, while C-3 was observed at 49.5 ppm in the 13 C-NMR spectrum. Noteworthy, despite all the attempts made, compound 7 was obtained in all cases, as a result of the E2 elimination of the 3-O-triflate group and the H-2 which are in antiperiplanar disposition.…”

Section: Scheme 1 Synthesis Of 1-o-acetyl-2-azido-46-o-benzylidene-2-deoxy-3-o-trifluoro Methanesulfonyl-β-d-allopyranosidementioning

confidence: 96%

“…Using GalSH (4) as nucleophile, 6 was obtained in 40% yield (Table 1, entry 3) when the reaction was carried out in the presence of 1.2 equivalents of Et3N at -10 ºC. The 1 H-NMR spectrum of 6 showed a triplet at 2.97 ppm, with J2,3  J3,4 = 10.8 Hz, diagnostic for the H-3, which correlated with a signal at 50.0 ppm in the 1 H- 13 C-HSQC NMR spectrum. On the other hand, when GlcASH (5) was used, the reaction required 2.4 equivalents of base and HMPA as co-solvent, giving 45% yield of 10 (Table 1, entry 5).…”

Section: Scheme 1 Synthesis Of 1-o-acetyl-2-azido-46-o-benzylidene-2-deoxy-3-o-trifluoro Methanesulfonyl-β-d-allopyranosidementioning

confidence: 96%

“…12 The mentioned disaccharide was alternatively synthesized from a 1,6anhydro-4-O-triflyl GlcNAc derivative and GlcNAcSNa in DMF. 13 Besides the SN2 mechanism to construct the thioglycosidic bond, alternative approaches were explored. The nucleophilic opening of a cyclic 2,3-sulfamidate was the key step to obtain the α-S-Fuc(13)GlcNAc thiodisaccharide.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of (1→3) Thiodisaccharides of GlcNAc and the Serendipitous Formation of 2,3-Dideoxy-(1→2)-thiodisaccharides through a Vinyl Azide Intermediate

2019

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The syntheses of β-S-GlcA(13)GlcNAc and β-S-Gal(13)GlcNAc thiodisaccharides were achieved by SN2 displacement of a triflate group allocated at 3-position of a convenient 2-azido-4,6-O-benzylidene-2-deoxy-β-D-allopyranose precursor, by the corresponding nucleophilic suitable protected thioaldoses derived from GlcA and Gal.The study of the reaction led to the finding that the vinylazide formed by the competitive E2 reaction of the mentioned triflate, was an interesting precursor of a new kind of 2,3dideoxy-2-azido-(12) thiodisaccharides, through an addition reaction. The determination of the stereochemistry of the new stereocenter at C-2 was achieved by NOESY experiments. Final protecting group manipulation of the (13) thiodisaccharides led to a family of derivatives that could be used as building blocks for the synthesis of more complex glycomimetics.

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Section: Scheme 1 Synthesis Of 1-o-acetyl-2-azido-46-o-benzylidene-2-deoxy-3-o-trifluoro Methanesulfonyl-β-d-allopyranosidementioning

confidence: 96%

Section: Scheme 1 Synthesis Of 1-o-acetyl-2-azido-46-o-benzylidene-2-deoxy-3-o-trifluoro Methanesulfonyl-β-d-allopyranosidementioning

confidence: 96%

Section: Introductionmentioning

confidence: 99%

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Synthesis of (1→3) Thiodisaccharides of GlcNAc and the Serendipitous Formation of 2,3-Dideoxy-(1→2)-thiodisaccharides through a Vinyl Azide Intermediate

2019

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“…Similarly, good yield of 77 (64%) was obtained by displacement of the anomeric bromide of 76 by the glucosamine 4-thiolate 75 [36]. The thiodisaccharides 74 and 77 are precursors of thioanalogs of nodulation (Nod) factors, potentially resistant to degradation by chitinases.…”

Section: I) Nucleophilic Displacement Of a Good Leaving Group In A Camentioning

confidence: 97%

Non-conventional Glycosidic Linkages: Syntheses and Structures of Thiooligosaccharides and Carbohydrates with Three-bond Glycosidic Connections

Varela¹

2006

COC

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Thiooligosaccharides display inhibitory activity against glycoside hydrolases and they constitute a valuable tool for structural biology. The construction of the interglycosidic linkage, in which the oxygen atom is replaced by sulfur, usually involves one of the following reactions: i) nucleophilic displacement of good leaving groups in a carbohydrate moiety by a sugar thiol, ii) Michael and Michael-type additions of sugar thiols to unsaturated acceptors, iii) ring-opening of aziridines and oxiranes by thiosugars, iv) enzyme-catalyzed couplings of thiosugar moieties. The application of these reactions for the syntheses of thiooligosaccharides are surveyed, and the biological activities of the resulting products briefly described. Carbohydrate structures incorporating three-bond glycosidic linkages with two heteroatoms are uncommon in Nature. The -N-O-interglycosidic bond in the oligosaccharide part of enediyne antibiotics is partly responsible for their potent antitumor activities. The disulfide bond which plays an essential role in proteins has recently been introduced as an interglycosidic connecting motif. The sulfenamide functionality is the sulfur analog of the hydroxylamine type glycosidic linkages in calicheamicins. Novel glycosylation strategies have recently been developed by taking advantage of unconventional, three-bond glycosidic linkages to construct neoglycoproteins and other glycoconjugates which are increasingly important tools in glycobiology and drug discovery. To explore conformational preferences and molecular flexibility in these structures NMR spectroscopy, chiroptical methods and X-ray crystallography are being used, supplemented by molecular modelling calculations. The structural features will be briefly discussed with relevance to biological interactions such as enzyme binding.

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“…Over the years, these and other classes of 2-NHTroc glycosyl donors have been used in glycoside and oligosaccharide synthesis: as trichloroacetimidates, 165,238,258,277, for the synthesis of pyruvated saccharide fragments, 280,304 Lipid A derivatives, 165,281,288,290,294,297,298,305,306 glycopeptides, 277,284,285 lactosaminyl donors, 282,307 Re-type lipopolysaccharides, 289 sialyl Lewis X glycolipids, 291,301 gangliosides, 292 peptidoglycan partial structures, 258,308 thiooligosaccharide analogues 286 of Nod factors, carbohydrate antigens, 295,302 sialyl-trimeric-Lewis X, 300 hyaluronan trisaccharides, 309 meonomycin A analogues, 310 and ceramidated GLA-60 293 derivatives; as fluorides, 282,311,312 for the synthesis of lactosaminyl donors, glycosylamines, 312 and tumor-associated antigen 311 Globo-H; as chlorides; 313 as thioglycosides, 283,286,[314][315][316][317][318][319][320][321][322]…”

Section: Alkoxycarbamoyl Derivatives 2-alkoxycarb-mentioning

confidence: 99%

Recent trends in the synthesis of O-glycosides of 2-amino-2-deoxysugars

Bongat

Demchenko

2007

Carbohydrate Research

199

110

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Synthesis of S-linked thiooligosaccharide analogues of Nod factors. Part 1: selectively N-protected 4-thiochitobiose precursors

Cited by 17 publications

References 11 publications

Synthesis of (1→3) Thiodisaccharides of GlcNAc and the Serendipitous Formation of 2,3-Dideoxy-(1→2)-thiodisaccharides through a Vinyl Azide Intermediate

Synthesis of (1→3) Thiodisaccharides of GlcNAc and the Serendipitous Formation of 2,3-Dideoxy-(1→2)-thiodisaccharides through a Vinyl Azide Intermediate

Non-conventional Glycosidic Linkages: Syntheses and Structures of Thiooligosaccharides and Carbohydrates with Three-bond Glycosidic Connections

Recent trends in the synthesis of O-glycosides of 2-amino-2-deoxysugars

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