(2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-(1->4)-7-O-acetyl-1,6-anhydro-2-O-benzyl-L-glycero-β-D-manno-heptopyranose | 215381-22-9

• 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: (2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-(1->4)-7-O-acetyl-1,6-anhydro-2-O-benzyl-L-glycero-β-D-manno-heptopyranose
• 英文别名: [(2R,3R,4S,5R,6S)-6-[[(1R,2S,3S,4S,5R,7S)-7-(acetyloxymethyl)-3-hydroxy-4-phenylmethoxy-6,8-dioxabicyclo[3.2.1]octan-2-yl]oxy]-3,4,5-tribenzoyloxyoxan-2-yl]methyl benzoate
• CAS: 215381-22-9
• 化学式: C₅₀H₄₆O₁₆
• 分子量: 902.906
• InChiKey: JWPGXPAGIJJPME-OIRPQEACSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.6
• 重原子数：
  66
• 可旋转键数：
  21
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  198
• 氢给体数：
  1
• 氢受体数：
  16

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-2-O-benzyl-L-glycero-β-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 0.67h， 以75%的产率得到(2,3,4,6,7-penta-O-benzoyl-L-glycero-α-D-manno-heptopyranosyl)-(1->3)-<(2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-(1->4)>-7-O-acetyl-1,6-anhydro-2-O-benzyl-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：

  7-O-acetyl-1,6-anhydro-L-glycero-β-D-manno-heptopyranose 在 camphor-10-sulfonic acid 、 silver trifluoromethanesulfonate 、 二正丁基氧化锡 、 溶剂黄146 作用下， 以 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 3.0h， 生成 (2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-(1->4)-7-O-acetyl-1,6-anhydro-2-O-benzyl-L-glycero-β-D-manno-heptopyranose
  参考文献：
  名称：

  支链三糖L-甘油-α-D-甘露聚糖基（1→3）-[β-D-吡喃葡萄糖基（（1→4）]-L-甘油-α-D-甘露聚糖-七糖的合成允许灵活访问奈瑟氏球菌和嗜血杆菌LPS核心结构

  摘要：

  摘要有效合成受保护的支链三糖（2'S，3'S）-（7-O-苄基-6-O-氯乙酰基-3,4-O-（2'，3'-二甲氧基丁烷-2'， 3′-二基）-2-氧-对甲氧基苄基-L-甘油-α-D-甘露聚糖-七吡喃糖基）-（1→3）-[（2,3,4,6-四-O-苯甲酰基-β -D-吡喃葡萄糖基）（（1→4）]-7-O-乙酰基-1,6-脱水-2-O-苄基-L-甘油-β-D-甘露聚糖描述了嗜血杆菌和奈瑟氏球菌LPSs的核心结构的合成。使用苄氧甲基氯或市售的乙烯基试剂通过格氏反应形成庚糖。脱水桥是通过用FeCl3处理6-OH甲基α-庚糖苷前体而形成的。保护基模式允许在第二个庚糖部分的2位，3位，4位和6位进行修饰，并且在无水桥乙酰化后，还可以在还原端进行延伸，

  DOI：

  10.1081/car-200044580

文献信息

• Synthesis of phosphorylated 3,4-branched trisaccharides corresponding to LPS inner core structures of Neisseria meningitidis and Haemophilus influenzae
  作者：Johan D.M. Olsson、Stefan Oscarson

  DOI：10.1016/j.carres.2010.03.006

  日期：2010.7

  spacer-equipped protected derivative of the common 3,4-branched diheptoside trisaccharide structure of the lipopolysaccharide core of Neisseria meningitidis and Haemophilus influenzae has been synthesized. The protecting group pattern installed allows regioselective introduction of phosphoethanolamine residues in the 3- and 6-position of the second heptose unit in accordance with native structures. From this intermediate

  2-（N-苄氧基羰基）氨基乙基7-O-乙酰基-6-O-烯丙基-2-O-苯甲酰基-4-O-苄基-3-O-氯乙酰基-1-甘油-α-d-manno-庚基吡喃糖基-（1-> 3）-[2,3,4,6-四-O-苯甲酰基-β-d-吡喃葡萄糖基-（1-> 4）] -6,7-二-O-乙酰基-2已经合成了脑膜炎奈瑟氏球菌和流感嗜血杆菌的3，4-支化二庚糖苷三糖结构的具有间隔基的被保护的衍生物-O-苄基-1-甘油-α-d-甘露聚糖-吡喃果糖苷。所安装的保护基图案允许根据天然结构在第二个庚糖单元的3位和6位区域选择性引入磷酸乙醇胺残基。