Chemical Synthesis Elucidates the Key Antigenic Epitope of the Autism‐Related Bacterium <i>Clostridium bolteae</i> Capsular Octadecasaccharide

Cai, Juntao; Hu, Jing; Qin, Chunjun; Li, Lingxin; Shen, Dacheng; Tian, Guangzong; Zou, Xiang; Seeberger, Peter H.; Yin, Jian

doi:10.1002/anie.202007209

Cited by 27 publications

(28 citation statements)

References 112 publications

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“…To our delight, the reaction still occurred with a high β/α ratio of 10 : 1 ( 1 J C,H =156 Hz for β‐anomer) under the stand conditions, giving the desired nonasaccharide 31 in 83 % yield. Nonasaccharide 31 could be used for further elongation as well as anomeric coupling of proper linker for potential vaccine studies [28] …”

Section: Resultsmentioning

confidence: 99%

“…Nonasaccharide 31 could be used for further elongation as well as anomeric coupling of proper linker for potential vaccine studies. [28] The concept of HAD has been used to rationalize the stereoselectivities in many reports. [3h, 31] Despite the support from many control reactions, [7,8,12] arguments still arise due to the lack of direct physical evidence such as a well-defined 1 H NMR monitoring of alcohol proton (OH), [1c, 32] particularly in a complex interaction system with bulky glycosyl acceptor.…”

Section: Methodsmentioning

confidence: 99%

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Direct Synthesis of 2,6‐Dideoxy‐β‐glycosides and β‐Rhamnosides with a Stereodirecting 2‐(Diphenylphosphinoyl)acetyl Group

et al. 2022

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Anomeric stereocontrol is usually one of the major issues in the synthesis of complex carbohydrates, particularly those involving β-configured 2,6-dideoxyglycoside and D/L-rhamnoside moieties. Herein, we report that 2-(diphenylphosphinoyl)acetyl is highly effective as a remote stereodirecting group in the direct synthesis of these challenging β-glycosides under mild conditions. A deoxy-trisaccharide as a mimic of the sugar chain of landomycin E was prepared stereospecifically in high yield. The synthetic potential was also highlighted in the synthesis of Citrobacter freundii O-antigens composed of a!] repeating unit, wherein the convergent assembly up to a nonasaccharide was realized with a strongly βdirecting trisaccharide donor. Variable-temperature NMR studies indicate the presence of intermolecular Hbonding between the donor and the bulky acceptor as direct spectral evidence in support of the concept of hydrogen-bond-mediated aglycone delivery.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Direct Synthesis of 2,6‐Dideoxy‐β‐glycosides and β‐Rhamnosides with a Stereodirecting 2‐(Diphenylphosphinoyl)acetyl Group

et al. 2022

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“…Upon assembly of the protected polysaccharide target, either by polymerization or chemical synthesis, the removal of the PGs often proved to be challenging. Aggregation [ 93 , 156 – 157 437 ], degradation (both during methanolysis [ 93 ] and hydrogenolysis [ 294 , 325 – 326 ]), substituent migration [ 322 , 438 ] or cleavage are among the most common issues encountered. The development of better PGs that can be removed quantitatively is highly desirable.…”

Section: Discussionmentioning

confidence: 99%

“…Recently, the synthesis of large bacterial polysaccharides containing ᴅ-Man, and ᴅ/ʟ-Rha mixed structures was reported [ 325 – 326 ]. The O -antigen of Bacteroides vulgatus consisted of alternating α(1–3)-ʟ-Rha and β(1–4)-ᴅ-Man linkages.…”

Section: Reviewmentioning

confidence: 99%

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Progress and challenges in the synthesis of sequence controlled polysaccharides

Fittolani¹,

Tyrikos‐Ergas²,

Vargová³

et al. 2021

Beilstein J. Org. Chem.

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The sequence, length and substitution of a polysaccharide influence its physical and biological properties. Thus, sequence controlled polysaccharides are important targets to establish structure–properties correlations. Polymerization techniques and enzymatic methods have been optimized to obtain samples with well-defined substitution patterns and narrow molecular weight distribution. Chemical synthesis has granted access to polysaccharides with full control over the length. Here, we review the progress towards the synthesis of well-defined polysaccharides. For each class of polysaccharides, we discuss the available synthetic approaches and their current limitations.

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Stereoselective Synthesis of the O‐antigen of A. baumannii ATCC 17961 Using Long‐Range Levulinoyl Group Participation

Duan

Nie

et al. 2023

Angewandte Chemie

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Herein, we described the first synthesis of the pentasaccharide and decasaccharide of the A. baumannii ATCC 17961 O-antigen for developing a synthetic carbohydrate-based vaccine against A. baumannii infection. The efficient synthesis of the rare sugar 2,3diacetamido-glucuronate was achieved using our recently introduced organocatalytic glycosylation method. We found, for the first time, that long-range levulinoyl group participation via a hydrogen bond can result in a significantly improved β-selectivity in glycosylations. This solves the stereoselectivity problem of highly branched galactose acceptors. The proposed mechanism was supported by control experiments and DFT computations. Benefiting from the long-range levulinoyl group participation strategy, the pentasaccharide donor and acceptor were obtained via an efficient [2 + 1 + 2] onepot glycosylation method and were used for the target decasaccharide synthesis.

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Chemical Synthesis Elucidates the Key Antigenic Epitope of the Autism‐Related Bacterium Clostridium bolteae Capsular Octadecasaccharide

Cited by 27 publications

References 112 publications

Direct Synthesis of 2,6‐Dideoxy‐β‐glycosides and β‐Rhamnosides with a Stereodirecting 2‐(Diphenylphosphinoyl)acetyl Group

Direct Synthesis of 2,6‐Dideoxy‐β‐glycosides and β‐Rhamnosides with a Stereodirecting 2‐(Diphenylphosphinoyl)acetyl Group

Progress and challenges in the synthesis of sequence controlled polysaccharides

Stereoselective Synthesis of the O‐antigen of A. baumannii ATCC 17961 Using Long‐Range Levulinoyl Group Participation

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