benzyl 4,6-O-<(S)-1-(methoxycarbonyl)ethylidene>-2,3-O-(1,1,3,3-tetraisopropyl-1,3-disiloxane-1,3-diyl)-α-D-glucopyranoside | 145835-76-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: benzyl 4,6-O-<(S)-1-(methoxycarbonyl)ethylidene>-2,3-O-(1,1,3,3-tetraisopropyl-1,3-disiloxane-1,3-diyl)-α-D-glucopyranoside
• 英文别名: benzyl 4,6-O-(S)-(1-methoxycarbonyl)ethylidene-2,3-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-α-D-glucopyranoside；methyl (1S,2R,4S,7R,9S,10R)-4-methyl-9-phenylmethoxy-12,12,14,14-tetra(propan-2-yl)-3,5,8,11,13,15-hexaoxa-12,14-disilatricyclo[8.5.0.02,7]pentadecane-4-carboxylate
• CAS: 145835-76-3
• 化学式: C₂₉H₄₈O₉Si₂
• 分子量: 596.866
• InChiKey: VFGMMBLYRNFFEU-HSZAMCLRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.56
• 重原子数：
  40
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.76
• 拓扑面积：
  90.9
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  benzyl 4,6-O-<(S)-1-(methoxycarbonyl)ethylidene>-2,3-O-(1,1,3,3-tetraisopropyl-1,3-disiloxane-1,3-diyl)-α-D-glucopyranoside 在 palladium on activated charcoal 吡啶 、 sodium hydroxide 、 氢气 作用下， 以 水 、 溶剂黄146 为溶剂， 反应 98.0h， 生成
  参考文献：
  名称：

  使用TIPS保护的糖苷构建寡糖的新型融合策略。耻垢分枝杆菌糖脂相关片段的合成

  摘要：

  将4，6- O-丙酮酸化的葡糖苷1分别转化为相应的葡糖基氟化物3和2，3 - O -TIPS保护的葡糖吡喃糖苷5。3和5的路易斯酸催化的偶合提供了丙酮酸化的二糖6，其中之一通过二糖供体8被进一步转化为耻垢分枝杆菌的二糖和三糖片段。

  DOI：

  10.1016/s0040-4039(00)60999-1
• 作为产物：
  描述：

  benzyl 2,3-di-O-benzoyl-4,6-O-<(S)-1-(methoxycarbonyl)ethylidene>-α-D-glucopyranoside 在 sodium methylate 咪唑 、 甲醇 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 25.0h， 生成 benzyl 4,6-O-<(S)-1-(methoxycarbonyl)ethylidene>-2,3-O-(1,1,3,3-tetraisopropyl-1,3-disiloxane-1,3-diyl)-α-D-glucopyranoside
  参考文献：
  名称：

  使用TIPS保护的糖苷构建寡糖的新型融合策略。耻垢分枝杆菌糖脂相关片段的合成

  摘要：

  将4，6- O-丙酮酸化的葡糖苷1分别转化为相应的葡糖基氟化物3和2，3 - O -TIPS保护的葡糖吡喃糖苷5。3和5的路易斯酸催化的偶合提供了丙酮酸化的二糖6，其中之一通过二糖供体8被进一步转化为耻垢分枝杆菌的二糖和三糖片段。

  DOI：

  10.1016/s0040-4039(00)60999-1

文献信息

• Synthetic studies toward pyruvate acetal-containing saccharides: En route to the efficient synthesis of Rhizobium-related exopolysaccharide fragments
  作者：Elisabeth Eckhardt、Thomas Ziegler

  DOI：10.1016/s0008-6215(05)80010-2

  日期：1994.11

  The disaccharide building block benzyl O-2,3-di-O-benzoyl-4,6-O-[(R)-1-(methoxycarbonyl) ethylidene]-beta-D-galactopyranosyl}-(1 --> 3)-2-O-benzoyl-4,6-O-[(S)-1-(methoxycarbonyl)ethylidene] -alpha-D-glucopyranoside (13), related to a Rhizobium exopolysaccharide, was prepared by coupling various 4,6-O-[(R)-1-(methoxycarbonyl)ethylidene]-D-galactosyl donors (benzoyl-protected chloride 1, pivaloyl-protected chloride 2, and benzoyl-protected fluorides 3 and 4, and trichloroacetimidate 5) with benzyl 2-O-benzoyl-4,6-O-[(S)-1-(methoxycarbonyl)ethylidene]-alpha-D-glucopyranoside (10) and the corresponding 2,3-O-tetraisopropyldisiloxane-protected glucoside 12. The best results, with respect to beta-selectivity and yield of the coupling, were obtained with 5 and 10 in dichloromethane. The beta-linked (13) and alpha-linked (14) disaccharides were efficiently converted via the 1-OH derivatives 17 and 21 into the corresponding trichloroacetimidates 18 and 22. The latter were used for the synthesis of the disaccharide ligands 4,6-(R)-pyruvate-beta-D-Galp-(1 --> 3)-4,6-(S)-pyruvate-beta-D-Glcp-O (CH2)(5)NH2 (20), and 4,6-(R)-pyruvate-alpha-D-Galp-(1 --> 3)-4,6-(S)-pyruvate-beta-D-Glcp-O(CH2)(5)NH2 (24). The corresponding tri- and tetra-saccharide derivatives 4,6-(R)-pyruvate-beta-D-Galp-(1 --> 3)-4,6-(S)-pyruvate-beta-D-Glcp-(1 --> 4)-beta-D-Glcp-O(CH2)(5)NH2 (28) and 4,6-(R)-pyruvate-beta-D-Galp-(1 --> 3)-4,6-(S)-pyruvate-beta-D-Glcp-(1 --> 4)-beta-D-Glcp-(1 --> 4)-beta-D-Glcp-O(CH2)(5)NH2 (36) were obtained similarly.
• A novel convergent strategy for the construction of oligosaccharides using TIPS-protected glycosides. Synthesis of fragments related to glycolipids of Mycobacterium smegmatis
  作者：Thomas Ziegler、Elisabeth Eckhardt

  DOI：10.1016/s0040-4039(00)60999-1

  日期：1992.10

  4,6-O-Pyruvylated glucosides 1 were converted to the corresponding glucosyl fluorides 3 and 2,3-O-TIPS-protected glucopyranosides 5, respectively. Lewis-acid-catalyzed coupling of 3 and 5 afforded the pyruvylated disaccharides 6 one of which was further converted via the dissacharide donor 8 to di- and trisaccharide fragments of Mycobacterium smegmatis.

  将4，6- O-丙酮酸化的葡糖苷1分别转化为相应的葡糖基氟化物3和2，3 - O -TIPS保护的葡糖吡喃糖苷5。3和5的路易斯酸催化的偶合提供了丙酮酸化的二糖6，其中之一通过二糖供体8被进一步转化为耻垢分枝杆菌的二糖和三糖片段。