allyl (2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl)-(1->4)-α-L-rhamnopyranoside | 236731-58-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: allyl (2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl)-(1->4)-α-L-rhamnopyranoside
• 英文别名: Bn(-2)[Bn(-3)][Bn(-4)][Bn(-6)]Glc(a1-4)Rha(a)-O-allyl；(2R,3R,4S,5R,6S)-6-methyl-2-prop-2-enoxy-5-[(2R,3R,4S,5R,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-yl]oxyoxane-3,4-diol
• CAS: 236731-58-1
• 化学式: C₄₃H₅₀O₁₀
• 分子量: 726.864
• InChiKey: YJUMJWQYRAVJRU-OHGRFQKISA-N

物化性质

• 沸点：
  813.3±65.0 °C(Predicted)
• 密度：
  1.25±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  53
• 可旋转键数：
  18
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  114
• 氢给体数：
  2
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  allyl (2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl)-(1->4)-α-L-rhamnopyranoside 在 palladium dichloride 三氟甲磺酸三甲基硅酯 、 camphor-10-sulfonic acid 、 sodium acetate 作用下， 以 乙醚 、 二氯甲烷 、 水 、 溶剂黄146 为溶剂， 反应 5.83h， 生成 (2-O-acetyl-3,4-di-O-benzyl-α-L-rhamnopyranosyl)-(1-3)-[(2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl)-(1-4)]-2-O-benzoyl-L-rhamnopyranose
  参考文献：
  名称：

  弗氏志贺氏菌血清型2a O特异性多糖的四糖和五糖片段的甲基糖苷的聚合合成

  摘要：

  支化的五糖，α-L-鼠李糖p - （1→3） - [α-d-GLC p - （1→4）] - α-L-鼠李糖p - （1→3）-β-d-GlcNAc的p - （1→2）-α-L-鼠李糖p（B（E）CDA）和相应的线性四糖（ECDA），这是一部分的痢疾杆菌血清型2A ø -抗原，合成为根据它们的甲基糖苷趋同的策略。合成分别依赖于使用合适的B（E）C和EC三氯乙酰亚胺酸酯供体，并且涉及带有合适的DA受体，该受体带有异亚丙基乙缩醛以阻断残基D的OH-4和OH-6 。还描述了用作模型的相关线性CDA-OMe三糖的制备。

  DOI：

  10.1016/s0957-4166(02)00580-3
• 作为产物：
  描述：

  allyl 2,3-O-isopropylidene-α-L-rhamnopyranoside 在 三氟甲磺酸三甲基硅酯 、 溶剂黄146 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 7.5h， 生成 allyl (2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl)-(1->4)-α-L-rhamnopyranoside
  参考文献：
  名称：

  弗氏志贺氏菌血清型2a O特异性多糖的四糖和五糖片段的甲基糖苷的聚合合成

  摘要：

  支化的五糖，α-L-鼠李糖p - （1→3） - [α-d-GLC p - （1→4）] - α-L-鼠李糖p - （1→3）-β-d-GlcNAc的p - （1→2）-α-L-鼠李糖p（B（E）CDA）和相应的线性四糖（ECDA），这是一部分的痢疾杆菌血清型2A ø -抗原，合成为根据它们的甲基糖苷趋同的策略。合成分别依赖于使用合适的B（E）C和EC三氯乙酰亚胺酸酯供体，并且涉及带有合适的DA受体，该受体带有异亚丙基乙缩醛以阻断残基D的OH-4和OH-6 。还描述了用作模型的相关线性CDA-OMe三糖的制备。

  DOI：

  10.1016/s0957-4166(02)00580-3

文献信息

• Novel O-acetylated decasaccharides
  申请人：Institut Pasteur

  公开号：EP2386563A1

  公开（公告）日：2011-11-16

  The present invention relates to diversely acetylated decasaccharides of formula (I) representative of two repeating units of Shigella flexneri serotype 2a O-antigen, conjugates and method of preparation thereof. These compounds exhibit antigenic properties and are particularly useful for the diagnosis of Shigella infection. wherein R1 and R2 are as defined in claim 1.

  本发明涉及式(I)的多样乙酰化十糖，代表志贺氏菌弗氏氏2a O-抗原的两个重复单元，以及其结合物和制备方法。这些化合物具有抗原性质，特别适用于志贺氏菌感染的诊断。 其中R1和R2如权利要求1中定义的。
• Non-stoichiometric O-acetylation of Shigella flexneri 2a O-specific polysaccharide: synthesis and antigenicity
  作者：Charles Gauthier、Pierre Chassagne、François-Xavier Theillet、Catherine Guerreiro、Françoise Thouron、Farida Nato、Muriel Delepierre、Philippe J. Sansonetti、Armelle Phalipon、Laurence A. Mulard

  DOI：10.1039/c3ob42586j

  日期：——

  Synthetic functional mimics of the O-antigen from Shigella flexneri 2a are seen as promising vaccine components against endemic shigellosis. Herein, the influence of the polysaccharide non-stoichiometric di-O-acetylation on antigenicity is addressed for the first time. Three decasaccharides, representing relevant internal mono- and di-O-acetylation profiles of the O-antigen, were synthesized from a

  来自弗氏志贺氏菌2a的O抗原的合成功能模拟物被认为是对抗地方性志贺氏菌病的有前途的疫苗成分。在此，首次解决了多糖非化学计量的二-O-乙酰化对抗原性的影响。从十个关键的保护性十糖合成了三个十糖，它们代表了O抗原的相关内部单-和二-O-乙酰化分布，其目的是定制后期的位点选择性O-乙酰化。后者通过涉及亚氨酸酯糖基化化学的收敛途径获得。对五种保护性mIgG的结合研究表明，没有一种乙酸盐能显着增加广泛的抗体识别能力。然而，五种抗体之一具有独特的结合模式。带IC50在微摩尔至亚微摩尔范围mIgG F22-4例示了显着的紧密结合抗体针对的医学重要性的中性多糖的多样化O-乙酰化和非O-乙酰化的片段。
• Blockwise Approach to Fragments of the O-Specific Polysaccharide of <i>Shigella </i><i>f</i><i>lexneri</i> Serotype 2a:  Convergent Synthesis of a Decasaccharide Representative of a Dimer of the Branched Repeating Unit¹
  作者：Frédéric Bélot、Karen Wright、Corina Costachel、Armelle Phalipon、Laurence A. Mulard

  DOI：10.1021/jo035125b

  日期：2004.2.1

  The D‘A‘B‘(E‘)C‘DAB(E)C decasaccharide representative of a dimer of a frame-shifted pentasaccharide repeating unit of the O-specific polysaccharide of Shigella flexneri 2a was synthesized as its methyl glycoside by condensing a pentasaccharide donor (D‘A‘B‘(E‘)C‘) and a pentasaccharide acceptor (DAB(E)C-OMe). Several convergent routes to these two building blocks, involving either the AB linkage or

  的d “甲”乙“ （E ” ）C ' DAB（E）C十糖代表的二聚物的帧偏移的五糖重复的O-特异性多糖的单元弗氏志贺菌2a中被冷凝合成作为它的甲基糖苷五糖给体（d '甲'乙' （E ' ）C “）和五糖受体（DAB（E）C -OMe）。通往这两个构建块的多条融合路线，涉及AB链接或BC链接作为断开位置，与线性策略相比进行了评估。后者是优选的。它基于三氯乙酰亚胺酸化学的使用。设计目标支链低聚糖，以探测保护性单克隆抗体在天然多糖分子水平上的识别。
• Synthesis of the Methyl Glycosides of a Di- and Two Trisaccharide Fragments Specific for the<i>Shigella flexneri</i>Serotype 2a<i>O</i>-Antigen
  作者：Laurence A. Mulard、Corina Costachel、Philippe J. Sansonetti

  DOI：10.1080/07328300008544123

  日期：2000.1

  The stereocontrolled synthesis of methyl alpha-D-glucopyranosyl-(1-->4)-alpha-L-rhamnopyranoside (EC, 1), methyl alpha-L-rhamnopyranosyl-(1-->3)-[alpha-D-glucopyra- osyl-(1-->4)]-alpha-L-rhamnopyranoside (B(E)C, 3) and methyl alpha-D-glucopyranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->3)-2-acetamido-2-deoxy-beta-D-glucopyranoside (ECD, 4) is described; these constitute the methyl glycosides of branched and linear fragments of the O-specific polysaccharide of Shigella flexneri serotype 2a. Emphasis was put on the construction of the 1,2-cis EC glycosidic linkage resulting in the selection of 2,3,4,6-tetra-O-benzyl-alpha-D-glucopyranosyl fluoride (8) as the donor. Condensation of methyl 2,3-O-isopropylidene-4-O-trimethylsilyloside-alpha-L-rhamnopyranoside (11) and 8 afforded the fully protected alpha E-disaccharide 20, as a common intermediate in the synthesis of 1 and 3, together with the corresponding beta E-anomer 21. Deacetalation and regioselective benzoylation of 20, followed by glycosylation with 2,3,4-tri-O-benzoyl-alpha-L-rhamnopyranosyl trichloroacetimidate (15) afforded the branched trisaccharide 25. Full deprotection of 20 and 25 afforded the targets 1 and 3, respectively. The corresponding beta E-disaccharide, namely, methyl beta-D-glucopyranosyl-(1-->4)-a-L-rhamnopyranoside (PEC, 2) was prepared analogously from 21. Two routes to trisaccharide 4 were considered. Route 1 involved the coupling of a precursor to residue E and a disaccharide CD. Route 2 was based on the condensation of an appropriate EC donor and a precursor to residue D. The former route afforded a 1:2 mixture of the alpha E and PE condensation products which could not be separated, neither at this stage, nor after deacetalation. In route 2, the required alpha E-anomer was isolated at the disaccharide stage and transformed into 2,3,4,6-tetra-O-benzyl-alpha-D-glucopyranosyl-(1-->4)-2,3-di-O-benzoyl-alpha-L-rhamnopyranosyl trichloroacetimidate (48) as the EC donor. Methyl 2-acetamido-2-deoxy-4,6-O-isopropylidene-beta-D-glucopyran-oside (19) was preferred to its benzylidene analogue as the precursor to residue D. Condensation of 19 and 48 and stepwise deprotection of the glycosylation product afforded the target 4.
• Convergent synthesis of the methyl glycosides of a tetra- and a pentasaccharide fragment of the Shigella flexneri serotype 2a O-specific polysaccharide
  作者：Fabienne Segat-Dioury、Laurence A. Mulard

  DOI：10.1016/s0957-4166(02)00580-3

  日期：2002.10

  The branched pentasaccharide, α-l-Rhap-(1→3)-[α-d-Glcp-(1→4)]-α-l-Rhap-(1→3)-β-d-GlcNAcp-(1→2)-α-l-Rhap (B(E)CDA) and the corresponding linear tetrasaccharide (ECDA), which are part of the Shigella flexneri serotype 2a O-antigen, were synthesized as their methyl glycosides according to a convergent strategy. The syntheses rely on the use of suitable B(E)C and EC trichloroacetimidate donors, respectively

  支化的五糖，α-L-鼠李糖p - （1→3） - [α-d-GLC p - （1→4）] - α-L-鼠李糖p - （1→3）-β-d-GlcNAc的p - （1→2）-α-L-鼠李糖p（B（E）CDA）和相应的线性四糖（ECDA），这是一部分的痢疾杆菌血清型2A ø -抗原，合成为根据它们的甲基糖苷趋同的策略。合成分别依赖于使用合适的B（E）C和EC三氯乙酰亚胺酸酯供体，并且涉及带有合适的DA受体，该受体带有异亚丙基乙缩醛以阻断残基D的OH-4和OH-6 。还描述了用作模型的相关线性CDA-OMe三糖的制备。