Synthesis and antigenic properties of C-7-modified Kdo mono- and disaccharide ligands and Kdo disaccharide interresidue lactones

Sixta, Georg; Wimmer, Kurt; Hofinger, Andreas; Brade, Helmut; Kosma, Paul

doi:10.1016/j.carres.2009.06.015

Cited by 6 publications

(5 citation statements)

References 25 publications

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“…Consequently, we found that when the glycosylation was catalyzed with IBr (2.4 equiv)/AgOTf (3.0 equiv) reagent system in CH 2 Cl 2 at −80 °C, previously utilized by Oscarson and co-workers for the activation of Kdo ethyl thioglycosides, the product 6d was obtained in an elevated 71% yield as α-anomer only (Table , entry 5). Then, the optimized reaction conditions were further applied to the coupling of other secondary glycosyl nucleophiles, including the disarmed peracetylated Gal alcohol 5e , rhamnose (Rha) 4-OH acceptor 5f , Kdo 4- and 7-OH acceptors 5g , h . As a result, the reaction of these substrates with 1c proceeded smoothly to yield, respectively, disaccharides 6e , f , (2 → 4)- and (2 → 7)-linked Kdo disaccharides 6g , h in good yield and also as a single α-ketoside (Table , entries 6–9).…”

Section: Results and Discussionmentioning

confidence: 99%

“…Then, the optimized reaction conditions were further applied to the coupling of other secondary glycosyl nucleophiles, including the disarmed peracetylated Gal alcohol 5e, 20 rhamnose (Rha) 4-OH acceptor 5f, 21 Kdo 4-and 7-OH acceptors 5g,h. 22 As a result, the reaction of these substrates with 1c proceeded smoothly to yield, respectively, disaccharides 6e,f, (2 → 4)-and…”

Section: Journal Of the American Chemical Societymentioning

confidence: 97%

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Stereodirecting Effect of C5-Carboxylate Substituents on the Glycosylation Stereochemistry of 3-Deoxy-d-manno-oct-2-ulosonic Acid (Kdo) Thioglycoside Donors: Stereoselective Synthesis of α- and β-Kdo Glycosides

et al. 2018

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The stereodirecting effect of C5-ester functions on the glycosylation stereoselectivity of 3-deoxy-d- manno-oct-2-ulosonic acid (Kdo) ethyl thioglycoside donors is presented. The coupling of 5- O-arylcarbonyl or acetyl protected Kdo thioglycosides with acceptors proceeds in an α-selective and high-yielding manner, leading to formation of α-linked Kdo glycosides products. On the other hand, the glycosylation stereoselectivity of the 5- O-2-quinolinecarbonyl (Quin) or 4-nitropicoloyl substituted Kdo thioglycoside donors is switchable: (1) The glycosylation of the 5- O-Quin carrying Kdo donors with primary glycosyl acceptors shows complete β-stereoselectivity, furnishing the corresponding β-glycosides in good-to-excellent yield. (2) The stereochemical outcome of the secondary acceptors with these Kdo donors is determined mainly by the stereoelectronic nature of the acceptor. Only or predominant α anomeric products are obtained when the Kdo donors couple with the disarmed or highly crowded secondary carbohydrate acceptors, while the selectivity may switch to predominant β in the glycosylation of the 5- O-4-nitropicoloyl carrying donor with more reactive secondary alcohols. The synthetic use of the newly developed Kdo donors 1c and 7b has been demonstrated by facile preparation of a structurally unique trisaccharide motif 19 which possesses both α- and β-Kdo glycosidic bonds.

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Section: Results and Discussionmentioning

confidence: 99%

Section: Journal Of the American Chemical Societymentioning

confidence: 97%

Stereodirecting Effect of C5-Carboxylate Substituents on the Glycosylation Stereochemistry of 3-Deoxy-d-manno-oct-2-ulosonic Acid (Kdo) Thioglycoside Donors: Stereoselective Synthesis of α- and β-Kdo Glycosides

et al. 2018

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“…The recent synthesis of Kdo analogues (Sixta et al, 2009) provides a convenient tool to probe the importance and the specificity of antibody-antigen interactions in the combining site of S25-2. The structure of S25-2 in complex with the antigen Kdo-(2!4)-Kdo (Fig.…”

Section: Resultsmentioning

confidence: 99%

“…Fractions containing Fab were dialyzed against 20 mM Tris pH 8.0 and concentrated to 10 mg ml À1 . The synthesis of the ligand used for cocrystallization, Kdo-(2!4)-5,6-dehydro-Kdo [sodium (3-deoxy--d-manno-oct-2-ulopyranosyl)onate-(2!4)-sodium (allyl-3,5-dideoxy--d-threo-oct-5-en-2-ulopyranosid)onate], has been reported by Sixta et al (2009).…”

Section: Production Of Antibody and Fab Fragmentsmentioning

confidence: 99%

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Exploring the cross-reactivity of S25-2: complex with a 5,6-dehydro-Kdo disaccharide

et al. 2012

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The near-germline antibody S25-2 exhibits a remarkable cross-reactivity for oligosaccharides containing the bacterial lipopolysaccharide carbohydrate 3-deoxy-D-manno-oct-2-ulosonic acid (Kdo). The recent synthesis of a variety of Kdo analogues permits a detailed structural analysis of the importance of specific interactions in antigen recognition by S25-2. The Kdo disaccharide analogue Kdo-(2→4)-5,6-dehydro-Kdo lacks a 5-OH group on the second Kdo residue and has been cocrystallized with S25-2. The structure reveals that the modification of the Kdo residue at position 5 results in a rearrangement of intramolecular hydrogen bonds in the antigen that allows it to assume a novel conformation in the antibody-combining site. The cross-reactive binding of S25-2 to this synthetic ligand highlights the adaptability of this antibody to non-natural synthetic analogues.

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Synthesis of Bacterial Cell Envelope Components

Ishiwata

Ito

2016

Glycochemical Synthesis

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Synthesis and antigenic properties of C-7-modified Kdo mono- and disaccharide ligands and Kdo disaccharide interresidue lactones

Cited by 6 publications

References 25 publications

Stereodirecting Effect of C5-Carboxylate Substituents on the Glycosylation Stereochemistry of 3-Deoxy-d-manno-oct-2-ulosonic Acid (Kdo) Thioglycoside Donors: Stereoselective Synthesis of α- and β-Kdo Glycosides

Stereodirecting Effect of C5-Carboxylate Substituents on the Glycosylation Stereochemistry of 3-Deoxy-d-manno-oct-2-ulosonic Acid (Kdo) Thioglycoside Donors: Stereoselective Synthesis of α- and β-Kdo Glycosides

Exploring the cross-reactivity of S25-2: complex with a 5,6-dehydro-Kdo disaccharide

Synthesis of Bacterial Cell Envelope Components

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