methyl (2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl)-(1->4)-2-O-benzoyl-α-L-rhamnopyranoside | 311778-89-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl)-(1->4)-2-O-benzoyl-α-L-rhamnopyranoside
• 英文别名: methyl 2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl-(1->4)-2-O-benzoyl-α-L-rhamnopyranoside
• CAS: 311778-89-9
• 化学式: C₄₈H₅₂O₁₁
• 分子量: 804.934
• InChiKey: XLKCASNHSITCAN-HQXYDUNTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.05
• 重原子数：
  59.0
• 可旋转键数：
  18.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  120.37
• 氢给体数：
  1.0
• 氢受体数：
  11.0

反应信息

• 作为反应物：
  描述：

  methyl (2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl)-(1->4)-2-O-benzoyl-α-L-rhamnopyranoside 在 palladium on activated charcoal 三氟甲磺酸三甲基硅酯 、 氢气 作用下， 以 乙醚 、 乙醇 、 溶剂黄146 为溶剂， 反应 72.0h， 生成 methyl (2,3,4-tri-O-benzoyl-α-L-rhamnopyranosyl)-(1->3)-[(α-D-glucopyranosyl)-(1->4)]-2-O-benzoyl-α-L-rhamnopyranoside
  参考文献：
  名称：

  Synthesis of the Methyl Glycosides of a Di- and Two Trisaccharide Fragments Specific for theShigella flexneriSerotype 2aO-Antigen

  摘要：

  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.

  DOI：

  10.1080/07328300008544123
• 作为产物：
  描述：

  [(3aR,4R,6S,7S,7aS)-4-methoxy-2,2,6-trimethyl-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-7-yl]oxy-trimethylsilane 在 三氟甲磺酸酐 、 camphor-10-sulfonic acid 、 水 、 三氟乙酸 作用下， 以 乙醚 、 二氯甲烷 、 氯仿 为溶剂， 反应 21.25h， 生成 methyl (2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl)-(1->4)-2-O-benzoyl-α-L-rhamnopyranoside
  参考文献：
  名称：

  Synthesis of the Methyl Glycosides of a Di- and Two Trisaccharide Fragments Specific for theShigella flexneriSerotype 2aO-Antigen

  摘要：

  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.

  DOI：

  10.1080/07328300008544123

文献信息

• Linear Synthesis of the Methyl Glycosides of Tetra- and Pentasaccharide Fragments Specific for the <i>Shigella flexneri</i> Serotype 2a <i>O</i>-Antigen
  作者：Corina Costachel、Philippe J. Sansonetti、Laurence A. Mulard

  DOI：10.1080/07328300008544139

  日期：2000.1.1

  glycosides of a branched tetra- and pentasaccharide fragments of the O-specific polysaccharide of Shigella flexneri serotype 2a, respectively. The chemoselective O-deacetylation at position 2B and/or 2A of key tri- and tetrasaccharide intermediates bearing a protecting group at position 2C was a limiting factor. As such a step occurred once in the synthesis of 4 and twice in the synthesis of 5, the regioselective

  从已知的甲基2,3,4,6-四-O-苄基-α-D-吡喃葡萄糖基-（1→4）-2 - O-苯甲酰基-α-L-鼠李糖吡喃糖苷开始逐步合成甲基α -L-鼠李吡喃糖基-（1→2）-α-L-鼠李吡喃糖基-（1→3）-[α-D-吡喃吡喃糖基-（1→4）]-α-L-鼠李糖吡喃糖苷（AB（E）C，4）和2-乙酰氨基-2-脱氧-β-D-吡喃吡喃糖基-（1→2）-α-L-鼠李糖吡喃糖基-（1→3）-[α -D-吡喃葡萄糖基-（（1→4）]-α-L-鼠李糖吡喃糖苷（DAB（E）C，5）。它们分别构成弗氏志贺氏菌血清型2a的O-特异性多糖的支链四糖和五糖片段的甲基糖苷。化学选择性O限制因子是在位置2 C带有保护基的关键三糖和四糖中间体的位置2 B和/或2 A上的β-脱乙酰基。作为这样的步骤发生一次的合成4在合成和两次5，区域选择性引入残基的甲一个上乙（E）C二醇前体（12），并且残余的d上的AB（E）C二醇还尝试