2-O-Methyl-4,7,8,9-tetra-O-acetyl-N-acetyl-alpha-D-neuraminic acid | 50669-91-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-O-Methyl-4,7,8,9-tetra-O-acetyl-N-acetyl-alpha-D-neuraminic acid
• 英文别名: (2R,4S,5R,6R)-5-acetamido-4-acetyloxy-2-methoxy-6-[(1S,2R)-1,2,3-triacetyloxypropyl]oxane-2-carboxylic acid
• CAS: 50669-91-5
• 化学式: C₂₀H₂₉NO₁₃
• 分子量: 491.449
• InChiKey: OACJSJXGBWIXRR-UMCYSPNLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  34
• 可旋转键数：
  14
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  190
• 氢给体数：
  2
• 氢受体数：
  13

反应信息

• 作为反应物：
  描述：

  甲醇 、 2-O-Methyl-4,7,8,9-tetra-O-acetyl-N-acetyl-alpha-D-neuraminic acid 在 三甲基硅烷化重氮甲烷 作用下， 以 苯 为溶剂， 反应 1.0h， 生成 methyl (methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-β-D-galacto-non-2-ulopyranosid)onate 、 methyl [methyl 4,7,8,9-tetra-O-acetyl-5-acetamido-3,5-dideoxy-α-D-glycero-D-galacto-non-2-ulopyranoside]onate
  参考文献：
  名称：

  Synthesis of Methyl and Allyl alpha-Glycosides of N-Acetylneuraminic Acid in the Absence of Added Promoter.

  摘要：

  Sialic acids, especially N-acetylneuraminic acid, are present (as alpha-glycosides) on biologically important glycolipids and glycoproteins. Synthesis of sialic acid-containing oligosaccharides is therefore a prerequisite for many glycobiological studies. Such syntheses often use simple sialyl glycosides as starting materials. Their preparation usually employs heavy metal salts or other toxic and/or expensive promoters.' As a consequence, only few of these methods are suitable for large-scale preparations.We wish to report a simple, alpha/beta-selective, and high-yielding preparative procedure for the methyl sialosides 5 and 6, and the allyl sialoside 7 (Scheme 1), that avoids the use of specially added promoter (although HCl liberated during the reaction probably promotes the reaction). A few examples of 'non-catalyzed' glycosylations with acetobromohexosides, leading to de-O-acetylated methyl glycosides, have been reported.(2) Furthermore, various bromo analogs of 4 were recently used for sialylation of methanol and benzyl alcohol in the absence of metal salt promoters (but in the presence of collidinium salt) to give glycosides in 70-95% yield, with an alp ratio of 1:1-9:1.(3)The known O-acetylated N-acetylneuraminic acid(4) (1) and methyl ester(5,6) (2) were treated separately with HCl/CH2Cl2 to give acetochloroneuraminic acid(4) (3) and methyl ester(5) (4) of 90-95% purity according to H-1 NMR. Compounds 3 and 4 were each dissolved in methanol and the mixtures were kept at room temperature. According to TLC analysis, compound 3 was consumed within 1 min, whereas compound 4 required a reaction time of 1 h. Three different batches of methanol were investigated, with virtually identical results.

  DOI：

  10.3891/acta.chem.scand.52-0141
• 作为产物：
  描述：

  N-acetyl-2,4,7,8,9-penta-O-acetyl-D-neuraminic acid 在 盐酸 作用下， 以 二氯甲烷 为溶剂， 反应 18.02h， 生成 2-O-Methyl-4,7,8,9-tetra-O-acetyl-N-acetyl-alpha-D-neuraminic acid
  参考文献：
  名称：

  Synthesis of Methyl and Allyl alpha-Glycosides of N-Acetylneuraminic Acid in the Absence of Added Promoter.

  摘要：

  Sialic acids, especially N-acetylneuraminic acid, are present (as alpha-glycosides) on biologically important glycolipids and glycoproteins. Synthesis of sialic acid-containing oligosaccharides is therefore a prerequisite for many glycobiological studies. Such syntheses often use simple sialyl glycosides as starting materials. Their preparation usually employs heavy metal salts or other toxic and/or expensive promoters.' As a consequence, only few of these methods are suitable for large-scale preparations.We wish to report a simple, alpha/beta-selective, and high-yielding preparative procedure for the methyl sialosides 5 and 6, and the allyl sialoside 7 (Scheme 1), that avoids the use of specially added promoter (although HCl liberated during the reaction probably promotes the reaction). A few examples of 'non-catalyzed' glycosylations with acetobromohexosides, leading to de-O-acetylated methyl glycosides, have been reported.(2) Furthermore, various bromo analogs of 4 were recently used for sialylation of methanol and benzyl alcohol in the absence of metal salt promoters (but in the presence of collidinium salt) to give glycosides in 70-95% yield, with an alp ratio of 1:1-9:1.(3)The known O-acetylated N-acetylneuraminic acid(4) (1) and methyl ester(5,6) (2) were treated separately with HCl/CH2Cl2 to give acetochloroneuraminic acid(4) (3) and methyl ester(5) (4) of 90-95% purity according to H-1 NMR. Compounds 3 and 4 were each dissolved in methanol and the mixtures were kept at room temperature. According to TLC analysis, compound 3 was consumed within 1 min, whereas compound 4 required a reaction time of 1 h. Three different batches of methanol were investigated, with virtually identical results.

  DOI：

  10.3891/acta.chem.scand.52-0141

文献信息

• A new approach to the synthesis of 5-N-acetyl-D-neuraminic acid α-ketosides
  作者：Volker Eschenfelder、Reinhard Brossmer

  DOI：10.1016/s0008-6215(00)83672-1

  日期：1980.1
• Synthesis of Methyl and Allyl alpha-Glycosides of N-Acetylneuraminic Acid in the Absence of Added Promoter.
  作者：Leonid O. Kononov、Göran Magnusson、Marina I. Ferrero、Cesare Rol、Giovanni V. Sebastiani、George W. Francis、József Szúnyog、Bengt Långström

  DOI：10.3891/acta.chem.scand.52-0141

  日期：——

  Sialic acids, especially N-acetylneuraminic acid, are present (as alpha-glycosides) on biologically important glycolipids and glycoproteins. Synthesis of sialic acid-containing oligosaccharides is therefore a prerequisite for many glycobiological studies. Such syntheses often use simple sialyl glycosides as starting materials. Their preparation usually employs heavy metal salts or other toxic and/or expensive promoters.' As a consequence, only few of these methods are suitable for large-scale preparations.We wish to report a simple, alpha/beta-selective, and high-yielding preparative procedure for the methyl sialosides 5 and 6, and the allyl sialoside 7 (Scheme 1), that avoids the use of specially added promoter (although HCl liberated during the reaction probably promotes the reaction). A few examples of 'non-catalyzed' glycosylations with acetobromohexosides, leading to de-O-acetylated methyl glycosides, have been reported.(2) Furthermore, various bromo analogs of 4 were recently used for sialylation of methanol and benzyl alcohol in the absence of metal salt promoters (but in the presence of collidinium salt) to give glycosides in 70-95% yield, with an alp ratio of 1:1-9:1.(3)The known O-acetylated N-acetylneuraminic acid(4) (1) and methyl ester(5,6) (2) were treated separately with HCl/CH2Cl2 to give acetochloroneuraminic acid(4) (3) and methyl ester(5) (4) of 90-95% purity according to H-1 NMR. Compounds 3 and 4 were each dissolved in methanol and the mixtures were kept at room temperature. According to TLC analysis, compound 3 was consumed within 1 min, whereas compound 4 required a reaction time of 1 h. Three different batches of methanol were investigated, with virtually identical results.