methyl (methyl 5-acetamido-7,8,9-tri-O-acetyl-4-C-methyl-3,4,5-trideoxy-β-D-glycero-D-galacto-2-nonulopyranosid)onate | 134258-68-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (methyl 5-acetamido-7,8,9-tri-O-acetyl-4-C-methyl-3,4,5-trideoxy-β-D-glycero-D-galacto-2-nonulopyranosid)onate
• CAS: 134258-68-7
• 化学式: C₂₀H₃₁NO₁₁
• 分子量: 461.466
• InChiKey: MDVQJXKBZRRPSH-ACAYHXBWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.14
• 重原子数：
  32.0
• 可旋转键数：
  9.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  152.76
• 氢给体数：
  1.0
• 氢受体数：
  11.0

反应信息

• 作为产物：
  描述：

  Methyl (methyl 5-acetamido-3,4,5-trideoxy-8,9-O-isopropylidene-4-C-methylene-β-D-manno-2-nonulopyranosid)onate 在 palladium on activated charcoal 吡啶 、 氢气 、 溶剂黄146 作用下， 以 异丙醇 为溶剂， 60.0 ℃ 、344.73 kPa 条件下， 反应 17.0h， 生成 methyl (methyl 5-acetamido-7,8,9-tri-O-acetyl-4-C-methyl-3,4,5-trideoxy-β-D-glycero-D-galacto-2-nonulopyranosid)onate
  参考文献：
  名称：

  Structural variations of N-acetylneuraminic acid, part 19: Synthesis of both epimeric pairs of the 4-C-methyl- and 4-deoxy-4-C-methyl- as well as of the ?-methylketoside of 4-deoxy-4-C-methylene-N-acetylneuraminic acid

  摘要：

  While the reaction of the 4-oxo-Neu 5 Ac derivative 2a with tributoxy methyl zirconate led exclusively to equatorial 4-C-methyl derivative 3a, the analogous reaction with tetramethyl zirconate yielded a 3:2 mixture of both diastereoisomers 3a and 4a. After removal of protecting groups the 5-acetamido-3,4-dideoxy-4-C-methyl-D-glycero-D-galacto-2-nonulosoic acid 5a and 5-acetamido-3,4-dideoxy-4-C-methyl-D-glycero-D-talo-2-nonulosonic acid 6 a were obtained. The 4-C-methylene derivative was prepared by treatment of the same 4-oxo-derivative with CH2I2/Zn/Cp2ZrCl2. Subsequent hydrogenation led to both epimeric 4-deoxy-4-C-methyl derivatives 8a and 9a. Final removal of protecting groups gave the 5-acetamido-3,4,5-trideoxy-4-C-methyl-D-glycero-D-galacto-2-nonulosonic acid 10a respectively the 5-acetamido-2,7-anhydro-4-C-methyl-3,4,5-trideoxy-D-glycero-D-talo-2-nonulosonic acid 11a. The beta-methylketosides of the 4-deoxy-4-C-methyl- (16) and 4-C-methylene-Neu 5 Ac (15) were prepared via the peracetylated derivatives to obtain modell substrates for enzymatic studies. Thus all free acids were tested for inhibition of CMP-sialate synthase. Only the 4-C-methylene compound 15 showed most unexpectedly a strong competitive inhibition of this enzyme.

  DOI：

  10.1007/bf00815172