Synthesis of S-linked thiooligosaccharide analogues of Nod factors: synthesis of new protected thiodisaccharide and thiotrisaccharide intermediates

Morais, Latino Loureiro; Bennis, Khalil; Ripoche, Isabelle; Liao, Liang; Auzanneau, France‐Isabelle; Gelas, Jacques

doi:10.1016/s0008-6215(03)00149-6

Cited by 8 publications

(8 citation statements)

References 17 publications

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“…Compound 80 was converted into the anomeric trichloroacetimidate, and treated with 1,6-anhydro-2-azido-3-O-benzyl-2-deoxy-β-D-glucopyranoside in the presence of BF3.OEt2, to give 81 in 57% yield, as an α:β mixture (ratio 1:4.7). This work shows that thiodisaccharide glycosyl donors behave quite differently from the analogous O-disaccharides used to synthesize nodulation factors [38].…”

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

confidence: 91%

“…For the introduction of sulfur and activation of the anomeric center 1-thioaldoses, instead of 1-thioacetates, (38), via the corresponding glycosyl bromide (39), that is converted into S-glycosylisothiouronium salt (40). Cleavage of the S-amidino group under basic conditions or with sodium sulfite, leads to the 1-thioaldose derivative 41 [25].…”

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

confidence: 99%

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

confidence: 91%

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

confidence: 99%

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

Varela¹

2006

COC

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“…Later, the synthesis of a trisaccharide having the thio‐linkage at the non‐reducing end was also reported by Gelas and co‐workers [51] . They first used the previously synthesised 1,6‐anhydro thiodisaccharide 9 to obtain trichloroacetimidate glycosyl donor 10 in a 3‐step sequence.…”

Section: General Strategies For the Access To Thiodisaccharides: The Hexnac Challengementioning

confidence: 92%

“…Later, the synthesis of a trisaccharide having the thiolinkage at the non-reducing end was also reported by Gelas and co-workers. [51] They first used the previously synthesised 1,6-anhydro thiodisaccharide 9 to obtain trichloroacetimidate glycosyl donor 10 in a 3-step sequence. In this case, an azido group was placed at C-2, as precursor of the acetamido substituent, a common strategy employed in the synthesis of HexNAc-containing oligosaccharides.…”

Section: Thioglycosylation Reactionsmentioning

confidence: 99%

“…Prepared thiodisaccharide 63 was then conveniently transformed into imidate 12 (Scheme 12), which was used as glycosyl donor in the synthesis of thiotrisaccharide 13 (Section 2.1.1, Scheme 3b). [51] Furthermore, Rye et al synthesised the S-β-GalNAc-(1! 4)-GlcA thiodisaccharide which is a mimetic of the repetitive unit of the chondroitin chain.…”

Section: S N 2 Reactionsmentioning

confidence: 99%

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Synthesis of Thiodisaccharides Bearing N‐Acetylhexosamine Residues: Challenges, Achievements and Perspectives

Cristófalo

Cano

Uhrig

2021

The Chemical Record

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Carbohydrate-protein interactions are involved in a myriad of biological processes. Thus, glycomimetics have arisen as one of the most promising synthetic targets to that end. Within the broad variety of glycomimetics, thiodisaccharides have proven to be excellent tools to study these processes, and even more, some of them unveiled interesting biological activities. This review brings together research made on the introduction of N-acetylhexosamine residues into thiodisaccharides to date, passing through classic substitution (as S N 2, thioglycosylation and ring-opening reactions) and addition (as thiol-ene coupling and Michael-type additions) reactions. Recent and interesting developments regarding addition reactions to vinyl azides, cross-coupling reactions and novel chemoenzymatic methods are also discussed.

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Studies Directed to the Synthesis of Oligochitosans – Preparation of Building Blocks and Their Evaluation in Glycosylation Studies

Hansen¹,

Skrydstrup²

2007

Eur J Org Chem

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Thioglucosaminides with four different N‐protecting groups, Troc, Phth, Alloc and PNZ could selectively be benzoylated at the C3 and C6‐hydroxy groups in good yields without the requirement for low‐temperature techniques. These reactions could be performed by refluxing a solution of the N‐protected amino sugars with benzoyl chloride, 4‐(dimethylamino)pyridine and pyridine in dichloromethane. The efficacy of these thioglycosides both as donors and acceptors for the construction of chitosans was evaluated. Whereas, the thioglycosides could be easily coupled to simple alcohols in excellent yields using the glycosylation promoting system N‐iodosuccinimide and TMS triflate, these conditions could not effectuate coupling to the C4‐hydroxy group possessing flanking benzoyl protecting groups. On the other hand, exploitation of Crich's O‐glycosylation conditions involving a glycosyl triflate intermediate provided two different 1,4‐linked disaccharides in good yields.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Synthesis of S-linked thiooligosaccharide analogues of Nod factors: synthesis of new protected thiodisaccharide and thiotrisaccharide intermediates

Cited by 8 publications

References 17 publications

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

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

Synthesis of Thiodisaccharides Bearing N‐Acetylhexosamine Residues: Challenges, Achievements and Perspectives

Studies Directed to the Synthesis of Oligochitosans – Preparation of Building Blocks and Their Evaluation in Glycosylation Studies

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