2,3-di-O-benzoyl-4,6-O-<1-(R)-methoxycarbonyl(ethylidene)>-α-D-galactopyranosyl trichloroacetimidate | 154460-36-3

• 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 trichloroacetimidate
• 英文别名: 2,3-di-O-benzoyl-4,6-O-<(R)-1-methoxycarbonylethylidene>-α-D-galactopyranosyl trichloroacetimidate；2,3-di-O-benzoyl-4,6-O-((R)-1-methoxycarbonylethylidene)-α-D-galactopyranosyl trichloroacetimidate
• CAS: 154460-36-3
• 化学式: C₂₆H₂₄Cl₃NO₁₀
• 分子量: 616.836
• InChiKey: MAUBBSNYSGCEIL-YSWPIYOHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.83
• 重原子数：
  40.0
• 可旋转键数：
  6.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  139.67
• 氢给体数：
  1.0
• 氢受体数：
  11.0

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 trichloroacetimidate 在 三氟甲磺酸三甲基硅酯 、 sodium methylate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 5.5h， 生成
  参考文献：
  名称：

  5-氨基戊基4，6-O-[（R）-1-羧乙叉基]-β-D-吡喃半乳糖苷的合成及其作为人血清淀粉样蛋白P亲和层析的配体。蛋白。

  摘要：

  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，

  DOI：

  10.1016/0008-6215(94)80063-4
• 作为产物：
  描述：

  allyl 2,3-di-O-benzoyl-4,6-O-benzylidene-α-D-galactopyranoside 在 三氟化硼乙醚 、 potassium carbonate 、 溶剂黄146 、 palladium dichloride 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 105.5h， 生成 2,3-di-O-benzoyl-4,6-O-<1-(R)-methoxycarbonyl(ethylidene)>-α-D-galactopyranosyl trichloroacetimidate
  参考文献：
  名称：

  5-氨基戊基4，6-O-[（R）-1-羧乙叉基]-β-D-吡喃半乳糖苷的合成及其作为人血清淀粉样蛋白P亲和层析的配体。蛋白。

  摘要：

  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，

  DOI：

  10.1016/0008-6215(94)80063-4
• 作为试剂：
  描述：

  苯甲酰氯 、 benzyl O-(2,4,6-tri-O-benzoyl-β-D-glucopyranosyl)-(1->3)-2-O-benzoyl-4,6-O-<(S)-1-methoxycarbonyl(ethylidene)>-α-D-glucopyranoside 在 吡啶 、 三氟甲磺酸三甲基硅酯 、 2,3-di-O-benzoyl-4,6-O-<1-(R)-methoxycarbonyl(ethylidene)>-α-D-galactopyranosyl trichloroacetimidate 作用下， 生成 (2S,4aR,6S,7R,8S,8aR)-7-Benzoyloxy-6-benzyloxy-2-methyl-8-((2S,3R,4S,5R,6R)-3,4,5-tris-benzoyloxy-6-benzoyloxymethyl-tetrahydro-pyran-2-yloxy)-hexahydro-pyrano[3,2-d][1,3]dioxine-2-carboxylic acid methyl ester 、 benzyl O-{2,3-di-O-benzoyl-4,6-O-[(R)-1-methoxycarbonyl(ethylidene)]-β-D-galactopyranosyl}-(1->3)-2,4,6-tri-O-benzoyl-β-D-glucopyranosyl-(1->3)-2-O-benzoyl-4,6-O-[(S)-1-methoxycarbonyl(ethylidene)]-α-D-glucopyranoside 、 benzyl O-{2,3-di-O-benzoyl-4,6-O-[(R)-1-methoxycarbonyl(ethylidene)]-α-D-galactopyranosyl}-(1->3)-2,4,6-tri-O-benzoyl-β-D-glucopyranosyl-(1->3)-2-O-benzoyl-4,6-O-[(S)-1-methoxycarbonyl(ethylidene)]-α-D-glucopyranoside
  参考文献：
  名称：

  Rhizobial saccharides. Part. 4. Unusual Reactivity of Pyruvated Glycosyl Donors during construction of rhizobial exopolysaccharide fragments

  摘要：

  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.

  DOI：

  10.1002/prac.19973390196

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.