(2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-(1->4)-7-O-acetyl-1,6-anhydro-3-O-benzoyl-L-glycero-β-D-manno-heptopyranose | 215381-21-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-(1->4)-7-O-acetyl-1,6-anhydro-3-O-benzoyl-L-glycero-β-D-manno-heptopyranose
• 英文别名: [(2R,3R,4S,5R,6S)-6-[[(1R,2R,3R,4S,5R,7S)-7-(acetyloxymethyl)-3-benzoyloxy-4-hydroxy-6,8-dioxabicyclo[3.2.1]octan-2-yl]oxy]-3,4,5-tribenzoyloxyoxan-2-yl]methyl benzoate
• CAS: 215381-21-8
• 化学式: C₅₀H₄₄O₁₇
• 分子量: 916.889
• InChiKey: JXWPTQWWDXDHOC-GOVDYUNUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  67
• 可旋转键数：
  21
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  215
• 氢给体数：
  1
• 氢受体数：
  17

反应信息

• 作为反应物：
  描述：

  ethyl 2,3,4,6,7-penta-O-benzoyl-1-thio-L-glycero-α-D-manno-heptopyranoside 、 (2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-(1->4)-7-O-acetyl-1,6-anhydro-3-O-benzoyl-L-glycero-β-D-manno-heptopyranose 在 N-碘代丁二酰亚胺 、 DMTST 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 以37%的产率得到(2,3,4,6,7-penta-O-benzoyl-L-glycero-α-D-manno-heptopyranosyl)-(1->2)-<(2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-(1->4)>-7-O-acetyl-1,6-anhydro-3-O-benzoyl-L-glycero-β-D-manno-heptopyranose
  参考文献：
  名称：

  Synthesis of a Branched Heptose- and Kdo-Containing Common Tetrasaccharide Core Structure of Haemophilus influenzae Lipopolysaccharides via a 1,6-Anhydro-l-glycero-β-d-manno-heptopyranose Intermediate

  摘要：

  The synthesis of a common tetrasaccharide core structure of Haemophilus influenzae lipopolysaccharides, beta-D-glucopyranosyl-(1-->4)-[L-glycero-alpha-D-manno-heptopyranosyl-(1-->3)]-L-glycero-alpha-D-manno-heptopyranosyl-(1-->5)-3-deoxy-alpha-D-manno-octulopyranoside and the trisaccharide beta-D-glucopyranosyl-(1-->4)-[L-glycero-alpha-D-manno-heptopyranosyl-(1-->3)]-L-glycero-alpha-D-manno-heptopyranoside is described. The oligosaccharides are synthesized as glycosides of a bifunctional spacer, 2-(4-aminophenyl)ethanol, to allow the subsequent formation of immunogenic glycoconjugates, which will be evaluated as well-defined glycoconjugate vaccine candidates. The syntheses of the 3,4-branched structures were accomplished using a 1,6-anhydro-L-glycero-beta-D-manno-heptopyranose intermediate to diminish the steric crowding between the 3- and 1-substituent. This intermediate was effectively synthesized from a mannose precursor via a stereoselective one-carbon elongation using a Barbier reaction (which was found to be more convenient than a Grignard reaction) and anhydro bridge formation through an internal glycosylation of a 6-O-trimethylsilylated ethyl thioheptoside using NIS/TfOH as a promoter. The 3- and 4-substituent were readily introduced into the 1,6-anhydro intermediate by glycosylation reactions using thioglycosides as donors and NIS/TfOH as a promoter, a task which has not been possible using accepters with equatorial 3,4-substituents. Acetolysis of the anhydro bridge followed by conversion into the ethyl thioglycoside afforded a trisaccharide donor, which, in NIS/TfOH-promoted couplings to the spacer and to a Kdo acceptor followed by deprotection, efficiently gave the two target compounds.

  DOI：

  10.1021/jo9808573
• 作为产物：
  描述：

  1,6-anhydro-2,3,4,7-tetra-O-benzyl-L-glycero-β-D-manno-heptopyranose 在 palladium on activated charcoal 2,4,6-三甲基吡啶 、 氢气 、 silver trifluoromethanesulfonate 、 二正丁基氧化锡 、 对甲苯磺酸 、 溶剂黄146 作用下， 以 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， -78.0~80.0 ℃ 、810.6 kPa 条件下， 反应 26.25h， 生成 (2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-(1->4)-7-O-acetyl-1,6-anhydro-3-O-benzoyl-L-glycero-β-D-manno-heptopyranose
  参考文献：
  名称：

  Synthesis of a Branched Heptose- and Kdo-Containing Common Tetrasaccharide Core Structure of Haemophilus influenzae Lipopolysaccharides via a 1,6-Anhydro-l-glycero-β-d-manno-heptopyranose Intermediate

  摘要：

  The synthesis of a common tetrasaccharide core structure of Haemophilus influenzae lipopolysaccharides, beta-D-glucopyranosyl-(1-->4)-[L-glycero-alpha-D-manno-heptopyranosyl-(1-->3)]-L-glycero-alpha-D-manno-heptopyranosyl-(1-->5)-3-deoxy-alpha-D-manno-octulopyranoside and the trisaccharide beta-D-glucopyranosyl-(1-->4)-[L-glycero-alpha-D-manno-heptopyranosyl-(1-->3)]-L-glycero-alpha-D-manno-heptopyranoside is described. The oligosaccharides are synthesized as glycosides of a bifunctional spacer, 2-(4-aminophenyl)ethanol, to allow the subsequent formation of immunogenic glycoconjugates, which will be evaluated as well-defined glycoconjugate vaccine candidates. The syntheses of the 3,4-branched structures were accomplished using a 1,6-anhydro-L-glycero-beta-D-manno-heptopyranose intermediate to diminish the steric crowding between the 3- and 1-substituent. This intermediate was effectively synthesized from a mannose precursor via a stereoselective one-carbon elongation using a Barbier reaction (which was found to be more convenient than a Grignard reaction) and anhydro bridge formation through an internal glycosylation of a 6-O-trimethylsilylated ethyl thioheptoside using NIS/TfOH as a promoter. The 3- and 4-substituent were readily introduced into the 1,6-anhydro intermediate by glycosylation reactions using thioglycosides as donors and NIS/TfOH as a promoter, a task which has not been possible using accepters with equatorial 3,4-substituents. Acetolysis of the anhydro bridge followed by conversion into the ethyl thioglycoside afforded a trisaccharide donor, which, in NIS/TfOH-promoted couplings to the spacer and to a Kdo acceptor followed by deprotection, efficiently gave the two target compounds.

  DOI：

  10.1021/jo9808573