methyl (2,3,4-tri-O-benzoyl-α-L-rhamnopyranosyl)-(1->3)-[(2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl)-(1->4)]-2-O-benzoyl-α-L-rhamnopyranoside | 311778-90-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: methyl (2,3,4-tri-O-benzoyl-α-L-rhamnopyranosyl)-(1->3)-[(2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl)-(1->4)]-2-O-benzoyl-α-L-rhamnopyranoside
• 英文别名: Bz(-2)[Bz(-3)][Bz(-4)]Rha(a1-3)[Bn(-2)[Bn(-3)][Bn(-4)][Bn(-6)]Glc(a1-4)][Bz(-2)]a-Rha1Me；[(2S,3S,4R,5R,6S)-4,5-dibenzoyloxy-6-[(2R,3R,4R,5S,6S)-3-benzoyloxy-2-methoxy-6-methyl-5-[(2R,3R,4S,5R,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-yl]oxyoxan-4-yl]oxy-2-methyloxan-3-yl] benzoate
• CAS: 311778-90-2
• 化学式: C₇₅H₇₄O₁₈
• 分子量: 1263.4
• InChiKey: QIFSDSMWMOQJNI-YVHWFHKMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.3
• 重原子数：
  93
• 可旋转键数：
  30
• 环数：
  11.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  198
• 氢给体数：
  0
• 氢受体数：
  18

反应信息

• 作为反应物：
  描述：

  methyl (2,3,4-tri-O-benzoyl-α-L-rhamnopyranosyl)-(1->3)-[(2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl)-(1->4)]-2-O-benzoyl-α-L-rhamnopyranoside 在 palladium on activated charcoal 氢气 作用下， 以 乙醇 、 溶剂黄146 为溶剂， 反应 72.0h， 以90%的产率得到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：

  甲基 2,3-O-异亚丙基-alpha-L-吡喃鼠李糖苷 在 吡啶 、 三氟甲磺酸酐 、 三氟甲磺酸三甲基硅酯 、 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 23.25h， 生成 methyl (2,3,4-tri-O-benzoyl-α-L-rhamnopyranosyl)-(1->3)-[(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

• 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.