1,6-di-O-acetyl-2-azido-3,4-di-O-benzyl-2-deoxy-α-D-mannopyranose | 497096-14-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,6-di-O-acetyl-2-azido-3,4-di-O-benzyl-2-deoxy-α-D-mannopyranose
• CAS: 497096-14-7
• 化学式: C₂₄H₂₇N₃O₇
• 分子量: 469.494
• InChiKey: LFNIPGXHEHYFCA-HUUMMWPTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.69
• 重原子数：
  34.0
• 可旋转键数：
  10.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  129.05
• 氢给体数：
  0.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  1,6-di-O-acetyl-2-azido-3,4-di-O-benzyl-2-deoxy-α-D-mannopyranose 在 二甲胺 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以100%的产率得到6-O-acetyl-2-azido-3,4-di-O-benzyl-2-deoxy-α-D-mannopyranose
  参考文献：
  名称：

  Towards a Synthetic Glycoconjugate Vaccine Against Neisseria meningitidis A

  摘要：

  Albumin conjugates of synthetic fragments of the capsular polysaccharide of the Gram-negative bacterium Neisseria meningitidis serogroup A were prepared. The fragments include monosaccharides 1 [alpha-D-ManpNAc(1--> 0)-(CH2)(2)NH2] and 2 [6-O-P(O)-(O-)(2)-alpha-D-ManpNAc-(1 --> O)-(CH2)(2)NH2] ,disaccharide 3 [alpha-D-ManpNAc[1-->O-P(O)(O-) --> 6]-alpha-D-ManpNAc(1 --> O)-(CH2)(2)NH2], and trisaccharide 4 [alpha-D-ManpNAc-[1 -->O-P(O)(O-)--> 6]-alpha-D-ManpNAc-[1 -->O-P(O)(O-)--> 6]-alpha-D-ManpNAc-(1 --> O)-(CH2)(2)NH2]. Two monosaccharide blocks were employed as key intermediates. The reduc-ing-end mannose unit featured the NHAc group at C-2, and contained the aminoethyl spacer as the aglycon for the final bioconjugation. The interresidual phosphodiester linkages were fashioned from an anomerically positioned H-phosphonate group in a 2-azido-man-nose building block. The spacer-linked saccharides 1-4 were N-acylated with hepta-4,6-dienoic acid and the resulting conjugated diene-equipped saccharides were subjected to Diels-Alder-type addition with maleimidobutyryl-group functionalized human serum albumin to form covalent conjugates containing up to 26 saccharide haptens per albumin molecule. Complete H-1, C-13, and P-31 NMR assignments for 1-4 are given. Antigenicity of the neoglycoconjugates containing 1-4 was demonstrated by a double immunodiffusion assay which indicated that a fragment as small as a monosaccharide is recognized by a polyclonal meningococcus group A antiserum and that the O-acetyl group(s) present in the natural capsular material is not essential for antigenicity.

  DOI：

  10.1002/1521-3765(20021004)8:19<4424::aid-chem4424>3.0.co;2-1
• 作为产物：
  描述：

  乙酸酐 、 methyl 2-azido-3,4-di-O-benzyl-2-deoxy-6-O-triphenylmethyl-α-D-mannopyranoside 在 硫酸 作用下， 反应 0.25h， 以56%的产率得到1,6-di-O-acetyl-2-azido-3,4-di-O-benzyl-2-deoxy-α-D-mannopyranose
  参考文献：
  名称：

  Towards a Synthetic Glycoconjugate Vaccine Against Neisseria meningitidis A

  摘要：

  Albumin conjugates of synthetic fragments of the capsular polysaccharide of the Gram-negative bacterium Neisseria meningitidis serogroup A were prepared. The fragments include monosaccharides 1 [alpha-D-ManpNAc(1--> 0)-(CH2)(2)NH2] and 2 [6-O-P(O)-(O-)(2)-alpha-D-ManpNAc-(1 --> O)-(CH2)(2)NH2] ,disaccharide 3 [alpha-D-ManpNAc[1-->O-P(O)(O-) --> 6]-alpha-D-ManpNAc(1 --> O)-(CH2)(2)NH2], and trisaccharide 4 [alpha-D-ManpNAc-[1 -->O-P(O)(O-)--> 6]-alpha-D-ManpNAc-[1 -->O-P(O)(O-)--> 6]-alpha-D-ManpNAc-(1 --> O)-(CH2)(2)NH2]. Two monosaccharide blocks were employed as key intermediates. The reduc-ing-end mannose unit featured the NHAc group at C-2, and contained the aminoethyl spacer as the aglycon for the final bioconjugation. The interresidual phosphodiester linkages were fashioned from an anomerically positioned H-phosphonate group in a 2-azido-man-nose building block. The spacer-linked saccharides 1-4 were N-acylated with hepta-4,6-dienoic acid and the resulting conjugated diene-equipped saccharides were subjected to Diels-Alder-type addition with maleimidobutyryl-group functionalized human serum albumin to form covalent conjugates containing up to 26 saccharide haptens per albumin molecule. Complete H-1, C-13, and P-31 NMR assignments for 1-4 are given. Antigenicity of the neoglycoconjugates containing 1-4 was demonstrated by a double immunodiffusion assay which indicated that a fragment as small as a monosaccharide is recognized by a polyclonal meningococcus group A antiserum and that the O-acetyl group(s) present in the natural capsular material is not essential for antigenicity.

  DOI：

  10.1002/1521-3765(20021004)8:19<4424::aid-chem4424>3.0.co;2-1

文献信息

• A process for the preparation of 6-O-acetyl-2-azido-3,4-di-O-benzyl-2-deoxy-D-glucopyranose
  申请人：Adamed sp. z o.o.

  公开号：EP2374809A1

  公开（公告）日：2011-10-12

  The invention relates to a process for the preparation of 6-O-acetyl-2-azido-3,4-di-O-benzyl-2-deoxy-D-glucopyranose, which process comprises reaction of 1,6-anhydro-2-azido-2-deoxy-D-glucopyranose with benzyl bromide in acetonitrile in the presence of solid sodium hydroxide to form 1,6-anhydro-2-azido-3,4-di-O-benzyl-2-deoxy-D-glucopyranose; subsequent reaction of 1,6-anhydro-2-azido-3,4-di-O-benzyl-2-deoxy-D-glucopyranose with acetic anhydride in the presence of trifluoroacetic acid to form 1,6-di-O-acetyl-2-azido-3,4-di-O-benzyl-2-deoxy-D-glucopyranose; and treatment of 1,6-di-O-acetyl-2-azido-3,4-di-O-benzyl-2-deoxy-D-glucopyranose with piperidine in THF. 6-0-Acetyl-2-azido-3,4-di-O-benzyl-2-deoxy-D-glucopyranose is useful as a building block for synthesis of glucosamine oligosaccharides.

  该发明涉及一种制备6-O-乙酰基-2-叠氮基-3,4-二-O-苄基-2-去氧-D-葡萄糖吡喃的方法，该方法包括将1,6-脱水-2-叠氮基-2-去氧-D-葡萄糖吡喃与苄溴在乙腈中，在固体氢氧化钠存在下反应，形成1,6-脱水-2-叠氮基-3,4-二-O-苄基-2-去氧-D-葡萄糖吡喃；随后将1,6-脱水-2-叠氮基-3,4-二-O-苄基-2-去氧-D-葡萄糖吡喃与乙酸酐在三氟乙酸存在下反应，形成1,6-二-O-乙酰基-2-叠氮基-3,4-二-O-苄基-2-去氧-D-葡萄糖吡喃；并用哌啶在THF中处理1,6-二-O-乙酰基-2-叠氮基-3,4-二-O-苄基-2-去氧-D-葡萄糖吡喃。6-O-乙酰基-2-叠氮基-3,4-二-O-苄基-2-去氧-D-葡萄糖吡喃可用作合成氨基葡萄糖寡糖的构建块。