2,3-di-O-benzoyl-4,6-O-<1-(R)-methoxycarbonyl(ethylidene)>-α-D-galactopyranosyl chloride | 138857-92-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: 2,3-di-O-benzoyl-4,6-O-<1-(R)-methoxycarbonyl(ethylidene)>-α-D-galactopyranosyl chloride
• 英文别名: 2,3-di-O-benzoyl-4,6-O-<(R)-1-methoxycarbonylethylidene>-α-D-galactopyranosyl chloride；(R)-2,3-di-O-benzoyl-4,6-O-(1-methoxycarbonylethylidene)-α-D-galactopyranosyl chloride；2,3-di-O-benzoyl-4,6-O-(1-methoxycarbonyl)ethylidene-α-D-galactopyranosyl chloride；methyl (2R,4aR,6R,7R,8S,8aS)-7,8-dibenzoyloxy-6-chloro-2-methyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxine-2-carboxylate
• CAS: 138857-92-8
• 化学式: C₂₄H₂₃ClO₉
• 分子量: 490.894
• InChiKey: JYBTWGYEWBGMJC-HJKOMNDMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.71
• 重原子数：
  34.0
• 可旋转键数：
  5.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  106.59
• 氢给体数：
  0.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  2,3-di-O-benzoyl-4,6-O-<1-(R)-methoxycarbonyl(ethylidene)>-α-D-galactopyranosyl chloride 在 palladium on activated charcoal silver silicate 、 3 A molecular sieve 、 氢气 作用下， 以 二氯甲烷 、 乙酸乙酯 为溶剂， 25.0 ℃ 、250.01 kPa 条件下， 反应 30.0h， 生成 O-<2,3-di-O-benzoyl-4,6-O-<(R)-1-(methoxycarbonyl)ethylidene>-β-D-galactopyranosyl>-(1<*>3)-2-O-benzoyl-4,6-O-<(S)-1-(methoxycarbonyl)ethylidene>-β-D-glucopyranose
  参考文献：
  名称：

  Synthetic studies toward pyruvate acetal-containing saccharides: En route to the efficient synthesis of Rhizobium-related exopolysaccharide fragments

  摘要：

  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.

  DOI：

  10.1016/s0008-6215(05)80010-2
• 作为产物：
  描述：

  1,2,3-O-benzoyl-α-D-galactopyranoside 在 zinc(II) chloride 1,1-二氯甲醚 、 nitrosonium tetrafluoroborate 作用下， 以 二氯甲烷 、 氯仿 为溶剂， 反应 5.0h， 生成 2,3-di-O-benzoyl-4,6-O-<1-(R)-methoxycarbonyl(ethylidene)>-α-D-galactopyranosyl chloride
  参考文献：
  名称：

  Ziegler, Thomas; Eckhardt, Elisabeth; Herold, Gerhard, Liebigs Annalen der Chemie, 1992, # 5, p. 441 - 452

  摘要：

  DOI：

文献信息

• Synthesis of 5-aminopentyl 4,6-O-[(R)-1-carboxyethylidene]-β-d-galactopyranoside and its use as a ligand for the affinity chromatography of human serum amyloid P protein
  作者：Thomas Ziegler、Elisabeth Eckhardt、Jochen Strayle、Helmut Herzog

  DOI：10.1016/0008-6215(94)80063-4

  日期：1994.2

  corresponding protected beta-D-galactoside 27, deblocking of which afforded the title compound 1. Binding of 1 to epoxypropyl-modified acrylamide beads gave an affinity adsorbent that was used to isolate serum amyloid P protein from human serum.

  一系列2,3-二-O-苯甲酰基-D-吡喃半乳糖苷，α-烯丙基（5），α-苄基（6），β-乙基-1-硫代（7），β-苯基-1-硫代（由相应的4，6-O-亚苄基衍生物制备8）和α-甲基（9），并用丙酮酸甲酯在乙腈中缩醛化，以非对映选择性得到2,3-二-O-苯甲酰基-4,6。 -O-[（R）-1-甲氧基羰基亚乙基] -D-吡喃半乳糖苷10-16。将后者转化为2，3-二-O-苯甲酰基-4，6-O-[（R）-1-甲氧基羰基亚乙基] -D-半乳糖吡喃糖基α-和β-三氯乙亚氨酸酯19和20，α-和β -氟化物21和22，α-溴化物23和α-氯化物24。这些供体（包括苯基1-硫代半乳糖苷14）与5-[（苄氧基羰基）氨基]戊醇反应，得到相应的受保护的β-D-半乳糖苷27，
• Diastereoselective formation of pyruvylated glycosides from partly protected sugars and methyl pyruvate
  作者：Thomas Ziegler、Elisabeth Eckhardt、Gerhard Herold

  DOI：10.1016/s0040-4039(00)60097-7

  日期：1992.7

  Various partly protected sugars (gluco-, manno-, and galactopyranosides) were acetalized with methyl pyruvate in moderate to good yield with BF3-etherate as the condensing reagent. Thus, (1-methoxycarbonyl)ethylidene glycosides were obtained diastereoselectivity.

  各种部分受保护的糖（葡萄糖基，甘露糖苷和半乳糖吡喃糖苷）以丙酮酸甲酯缩醛化，并以BF 3-醚酸酯为缩合试剂。因此，获得了（1-甲氧基羰基）亚乙基糖苷的非对映选择性。
• Rhizobial saccharides. Part. 4. Unusual Reactivity of Pyruvated Glycosyl Donors during construction of rhizobial exopolysaccharide fragments
  作者：Thomas Ziegler、Elisabeth Eckhardt

  DOI：10.1002/prac.19973390196

  日期：——

  Two pyruvated galactosyl donors, 2,3-di-O-benzoyl-4,6-0-[1-(R)-methoxycarbonyl(ethylidene)]-alpha-D-galactopyranosyl chloride (6) and trichloroacetimidate 13, were coupled to position 3 of suitably protected mono and disaccharide benzyl glucoside accepters. For both donors, an unusual high content of the alpha-(1-->3)-linked products was obtained. The corresponding beta-(1-->3)-linked di- and trisaccharides are related to exopolysaccharides of Rhizobium leguminosarum.