Methyl (methyl 5-acetamido-3,4,5-trideoxy-8,9-O-isopropylidene-4-C-methylene-β-D-manno-2-nonulopyranosid)onate | 130264-73-2

• 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-3,4,5-trideoxy-8,9-O-isopropylidene-4-C-methylene-β-D-manno-2-nonulopyranosid)onate
• 英文别名: methyl (methyl 5-acetamido-3,5-dideoxy-4-C-methylene-8,9-O(methylethylidene)-β-D-manno-2-nonulopyranosid)onate；methyl (methyl-5-acetamido-4-C-methylene-8,9-O-(methyl-ethylidene)-3,5-dideoxy-β-D-manno-2-nonulopyranosidon)；methyl [methyl-5-acetamido-4-C-methylene-8,9-O-(methyl-ethylidene)-3,5-dideoxy-β-D-manno-2-nonulopyranosidon]；methyl (2S,5R,6R)-5-acetamido-6-[(S)-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-hydroxymethyl]-2-methoxy-4-methylideneoxane-2-carboxylate
• CAS: 130264-73-2
• 化学式: C₁₇H₂₇NO₈
• 分子量: 373.403
• InChiKey: JJKGUAKUYMRDFB-LYUDMSCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.76
• 拓扑面积：
  113
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  Methyl (methyl 5-acetamido-3,4,5-trideoxy-8,9-O-isopropylidene-4-C-methylene-β-D-manno-2-nonulopyranosid)onate 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 5.0h， 以70%的产率得到methyl (3R,4S,5R,7S)-4-acetamido-5-[(S)-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-hydroxymethyl]-7-methoxy-1,6-dioxaspiro[2.5]octane-7-carboxylate
  参考文献：
  名称：

  Synthesis of C-4-disubstituted analogues of N-acetylneuraminic acid

  摘要：

  通过亲核打开乙酰基-4,4′-无水神经氨酸衍生物 6 和 7 中的环氧化物环，合成了一些新型的 N-乙酰基神经氨酸 C-4 二取代类似物。这样就得到了叠氮化物 8、甲基醚 9、腈 10 和 N-乙酰神经氨酸甲酯的 8,9-异亚丙基化 β-甲基酮苷的氯化物 11，收率为中等至良好。

  DOI：

  10.1039/p19960002817
• 作为产物：
  描述：

  二碘甲烷 、 methyl-5-acetamido-8,9-O-(1'-methyl-ethylidene)-3,5-dideoxy-β-D-manno-2,4-nonodiulopyranosidonic acid methyl ester 在 二氯二茂锆 、 锌 作用下， 生成 Methyl (methyl 5-acetamido-3,4,5-trideoxy-8,9-O-isopropylidene-4-C-methylene-β-D-manno-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

文献信息

• Synthesis of the epimeric pair of 4-deoxy-4-(R)- and 4-deoxy-4-(S)-C-methyl-n-acetylneuraminic acid
  作者：Michael Hartmann、Erich Zbiral

  DOI：10.1016/0040-4039(90)80171-h

  日期：1990.1
• HARTMANN, MICHAEL;ZBIRAL, ERICH, TETRAHEDRON LETT., 31,(1990) N0, C. 2875-2878
  作者：HARTMANN, MICHAEL、ZBIRAL, ERICH

  DOI：——

  日期：——
• Synthesis of C-4-disubstituted analogues of N-acetylneuraminic acid
  作者：Darrin R. Groves、Mark Von Itzstein

  DOI：10.1039/p19960002817

  日期：——

  The synthesis of some novel C-4-disubstituted analogues of N-acetylneuraminic acid has been achieved by nucleophilic opening of the epoxide ring in the acetyl-4,4′-anhydroneuraminic acid derivatives 6 and 7. This has provided the azide 8, the methyl ether 9, the nitrile 10 and the chloride 11 of the 8,9-isopropylidenated β-methyl ketoside of methyl N-acetylneuraminate in moderate to good yields.

  通过亲核打开乙酰基-4,4′-无水神经氨酸衍生物 6 和 7 中的环氧化物环，合成了一些新型的 N-乙酰基神经氨酸 C-4 二取代类似物。这样就得到了叠氮化物 8、甲基醚 9、腈 10 和 N-乙酰神经氨酸甲酯的 8,9-异亚丙基化 β-甲基酮苷的氯化物 11，收率为中等至良好。
• 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
  作者：Michael Hartmann、Rudolf Christian、Erich Zbiral

  DOI：10.1007/bf00815172

  日期：——

  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.