2,3,5,6-tetra-O-benzyl-β-D-galactofuranosyl trichloroacetimidate

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3,5,6-tetra-O-benzyl-β-D-galactofuranosyl trichloroacetimidate
• 英文别名: O-(2,3,5,6-tetra-O-benzyl-β-D-galactofuranosyl)trichloroacetimidate；Bn(-2)[Bn(-3)][Bn(-5)][Bn(-6)]Galf(b)-O-C(NH)CCl3；[(2S,3R,4S,5S)-5-[(1R)-1,2-bis(phenylmethoxy)ethyl]-3,4-bis(phenylmethoxy)oxolan-2-yl] 2,2,2-trichloroethanimidate
• 化学式: C₃₆H₃₆Cl₃NO₆
• 分子量: 685.044
• InChiKey: ATDJBJPTDDOWIJ-YODGASFJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.5
• 重原子数：
  46
• 可旋转键数：
  16
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  79.2
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2,3,5,6-tetra-O-benzyl-β-D-galactofuranosyl trichloroacetimidate 在 三氟甲磺酸三甲基硅酯 、 methyl 3-O-benzoyl-4, 6-O-benzylidene-α-D-mannopyranoside 作用下， 以 乙醚 为溶剂， 以45%的产率得到2,3,5,6-tetra-O-benzyl-N-trichloroacetyl-α-D-galactofuranosylamine
  参考文献：
  名称：

  Influence of the solvent in low temperature glycosylations with O-(2,3,5,6-tetra-O-benzyl-β-d-galactofuranosyl) trichloroacetimidate for 1,2-cis α-d-galactofuranosylation

  摘要：

  Glycosylation studies for the construction of 1,2-cis alpha-linkages with O-(2,3,5,6-tetra-O-benzyl-beta-D-galactofuranosyl) trichloroacetimidate (1) and several acceptors, including D-mannosyl and L-rhamnosyl derivatives were performed. The reactions were conducted at low temperatures using CH2Cl2, Et2O, and acetonitrile as solvents. A non-participating solvent such as CH2Cl2 at 78 degrees C, favored the alpha-D-configuration. In contrast, acetonitrile strongly favored the beta-D-configuration, whereas no selectivities were observed with Et2O. The use of thiophene as an additive did not enhance the alpha-D-selectivity as in the pyranose counterpart. Although selectivities strongly depended on the acceptor, trichloroacetimidate 1 constitutes a valuable donor for the synthesis of alpha-D-Galf-(1 -> 2)-L-Rha and alpha-D-Galf-(1 -> 6)-D-Man. As these motifs are present in pathogenic microorganisms, these procedures described here are useful for the straightforward synthesis of natural oligosaccharides. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2011.04.005
• 作为产物：
  描述：

  2,3,5,6-tetra-O-benzyl-D-galactofuranose 、 三氯乙腈 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 2,3,5,6-tetra-O-benzyl-β-D-galactofuranosyl trichloroacetimidate 、 2,3,5,6-tetra-O-benzyl-α-D-galactofuranosyl trichloroacetimidate
  参考文献：
  名称：

  α-d-Galf-（1→2）-d-半乳糖醇和α-d-Galf-（1→2）[β-d-Galf-（1→3）]-d-半乳糖醇的寡糖衍生物拟杆菌分解纤维素糖蛋白

  摘要：

  摘要描述了通过还原性β-消除从拟杆菌细菌和热纤梭菌的糖蛋白中分离得到的α-d-半呋喃呋喃糖基-（1→2）-d-半乳糖醇的合成方法。采用了通过三氯乙亚氨酸酯方法选择性糖基化1，4-内酯的方法。还报道了α-d-Gal f-（1→2）[β-d-Gal f-（1→3）]-d -Galol的合成，其在两个端基异构构型中均包含Gal f单元。这些是最早在天然产物中发现的具有α-d -Gal f的合成寡糖。

  DOI：

  10.1016/j.carres.2006.07.013

文献信息

• Synthesis of α-d-Galf-(1→2)-d-galactitol and α-d-Galf-(1→2)[β-d-Galf-(1→3)]-d-galactitol, oligosaccharide derivatives from Bacteroides cellulosolvens glycoproteins
  作者：Lucía Gandolfi-Donadío、Gabriel Gola、Rosa M. de Lederkremer、Carola Gallo-Rodriguez

  DOI：10.1016/j.carres.2006.07.013

  日期：2006.11

  Abstract The synthesis of α- d -galactofuranosyl-(1→2)- d -galactitol, which has been isolated by reductive β-elimination from glycoproteins of Bacteroides cellulosolvens and Clostridium thermocellum , is described. The approach of selective glycosylation of an aldono-1,4-lactone by the trichloroacetimidate method was employed. The synthesis of α- d -Gal f -(1→2)[β- d -Gal f -(1→3)]- d -Galol, that

  摘要描述了通过还原性β-消除从拟杆菌细菌和热纤梭菌的糖蛋白中分离得到的α-d-半呋喃呋喃糖基-（1→2）-d-半乳糖醇的合成方法。采用了通过三氯乙亚氨酸酯方法选择性糖基化1，4-内酯的方法。还报道了α-d-Gal f-（1→2）[β-d-Gal f-（1→3）]-d -Galol的合成，其在两个端基异构构型中均包含Gal f单元。这些是最早在天然产物中发现的具有α-d -Gal f的合成寡糖。
• Influence of the solvent in low temperature glycosylations with O-(2,3,5,6-tetra-O-benzyl-β-d-galactofuranosyl) trichloroacetimidate for 1,2-cis α-d-galactofuranosylation
  作者：Gabriel Gola、Mariano J. Tilve、Carola Gallo-Rodriguez

  DOI：10.1016/j.carres.2011.04.005

  日期：2011.9

  Glycosylation studies for the construction of 1,2-cis alpha-linkages with O-(2,3,5,6-tetra-O-benzyl-beta-D-galactofuranosyl) trichloroacetimidate (1) and several acceptors, including D-mannosyl and L-rhamnosyl derivatives were performed. The reactions were conducted at low temperatures using CH2Cl2, Et2O, and acetonitrile as solvents. A non-participating solvent such as CH2Cl2 at 78 degrees C, favored the alpha-D-configuration. In contrast, acetonitrile strongly favored the beta-D-configuration, whereas no selectivities were observed with Et2O. The use of thiophene as an additive did not enhance the alpha-D-selectivity as in the pyranose counterpart. Although selectivities strongly depended on the acceptor, trichloroacetimidate 1 constitutes a valuable donor for the synthesis of alpha-D-Galf-(1 -> 2)-L-Rha and alpha-D-Galf-(1 -> 6)-D-Man. As these motifs are present in pathogenic microorganisms, these procedures described here are useful for the straightforward synthesis of natural oligosaccharides. (C) 2011 Elsevier Ltd. All rights reserved.
• Convergent Synthesis of Oligosaccharide Fragments Corresponding to the Cell Wall <i>O</i> -Polysaccharide of <i>Salmonella enterica</i> O53
  作者：Debashis Dhara、Anup Kumar Misra

  DOI：10.1002/open.201500102

  日期：2015.12

  oligosaccharides. The development of synthetic strategies to prepare glycoconjugate derivatives against pathogenic bacterial strains is therefore of great interest. Oligosaccharide fragments corresponding to the repeat unit of the cell wall O‐antigen of Salmonella enterica strain O53 were synthesized in good yield. Sequential and block glycosylation strategies were used for the synthesis of the target compounds

  常规的糖缀合物疫苗是使用从细菌发酵中分离的多糖制备的，这种方法具有一些重大缺陷，例如处理活细菌菌株，存在生物杂质以及寡糖表位结构的批间差异。但是，在许多情况下，已经显示出与蛋白质缀合的适当结构的合成片段可能是一种有效的疫苗，可以规避使用全长寡糖的缺点。因此，制备针对病原性细菌菌株的糖缀合物衍生物的合成策略的发展引起了极大的兴趣。对应于肠沙门氏菌细胞壁O抗原重复单元的寡糖片段以高产率合成了O53菌株。顺序和嵌段糖基化策略用于目标化合物的合成。在合成策略中使用了许多最新开发的反应条件。还针对多个糖基化步骤开发了一个单锅反应方案。所有糖基化反应的立体选择性结果都非常好。