ethyl (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)>-6,7-di-O-acetyl-3-O-benzoyl-1-thio-L-glycero-α-D-manno-heptopyranose | 215381-25-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: ethyl (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)>-6,7-di-O-acetyl-3-O-benzoyl-1-thio-L-glycero-α-D-manno-heptopyranose
• 英文别名: Bz(-2)[Bz(-3)][Bz(-4)][Bz(-6)][Bz(-7)]LDManHep(a1-2)[Bz(-2)[Bz(-3)][Bz(-4)][Bz(-6)]Glc(b1-4)][Bz(-3)]LDManHep6Ac7Ac(a)-SEt；[(2R,3R,4S,5R,6S)-3,4,5-tribenzoyloxy-6-[(2R,3S,4S,5S,6R)-4-benzoyloxy-2-[(1S)-1,2-diacetyloxyethyl]-6-ethylsulfanyl-5-[(2R,3S,4S,5R,6R)-3,4,5-tribenzoyloxy-6-[(1S)-1,2-dibenzoyloxyethyl]oxan-2-yl]oxyoxan-3-yl]oxyoxan-2-yl]methyl benzoate
• CAS: 215381-25-2
• 化学式: C₉₆H₈₄O₂₉S
• 分子量: 1733.77
• InChiKey: GSBMICUQWOBPCB-OLBFUHAQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  16.5
• 重原子数：
  126
• 可旋转键数：
  45
• 环数：
  13.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  387
• 氢给体数：
  0
• 氢受体数：
  30

反应信息

• 作为反应物：
  描述：

  methyl <2-(4-trifluoroacetamidophenyl)ethyl 4-O-benzyl-3-deoxy-7,8-O-isopropylidene-α-D-manno-oct-2-ulopyranosid>onate 、 ethyl (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)>-6,7-di-O-acetyl-3-O-benzoyl-1-thio-L-glycero-α-D-manno-heptopyranose 在 N-碘代丁二酰亚胺 、 三氟甲磺酸 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以71%的产率得到methyl <2-(4-trifluoroacetamidophenyl)ethyl (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)>-(6,7-di-O-acetyl-3-O-benzoyl-L-glycero-α-D-manno-heptopyranosyl)-(1->5)-4-O-ben...
  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：

  乙硫醇 、 (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)>-1,6,7-tri-O-acetyl-3-O-benzoyl-L-glycero-α-D-manno-heptopyranose 在 三氟化硼乙醚 作用下， 以83%的产率得到ethyl (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)>-6,7-di-O-acetyl-3-O-benzoyl-1-thio-L-glycero-α-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