Methyl-(methyl-5-acetamido-3,5-dideoxy-D-glycero-α-D-talo-nonulopyranosid)onat | 140195-54-6

• 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-3,5-dideoxy-D-glycero-α-D-talo-nonulopyranosid)onat
• 英文别名: methyl (2R,4R,5R,6R)-5-acetamido-4-hydroxy-2-methoxy-6-[(1R,2R)-1,2,3-trihydroxypropyl]oxane-2-carboxylate
• CAS: 140195-54-6
• 化学式: C₁₃H₂₃NO₉
• 分子量: 337.327
• InChiKey: JKTJXQQVMKZKQA-JGTVTFMFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -3.13
• 重原子数：
  23.0
• 可旋转键数：
  6.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  154.78
• 氢给体数：
  5.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  Methyl-(methyl-5-acetamido-3,5-dideoxy-D-glycero-α-D-talo-nonulopyranosid)onat 在 sodium hydroxide 作用下， 反应 5.0h， 以83.3%的产率得到Ammonium-(methyl-5-acetamido-3,5-dideoxy-D-glycero-α-D-talo-2-nonulo-pyranosid)onat
  参考文献：
  名称：

  Strukturelle Abwandlungen an N-Acetylneuramins�ure, 25. Mitt.: Synthese von Methyl-2-?-glycosiden von 4-epi-, 7-epi-, 8-epi- und 7,8-bis-epi-N-Acetylneuramins�ure

  摘要：

  The alpha-methylketoside of N-acetylneuraminic acid methylester (4) is transformed via the deacetylated compound 5 into the 9,8-O-isopropylidenderivative 6 which could be oxidized regioselectivity by RuO4 to the corresponding 4-oxo-sialic acid analogue 7. Reduction with the borane-ammonia complex produces a 1:1 mixture of 6 and the desired alpha-methylketoside of 9,8-O-isopropyliden-4-epi-N-acetyl-neuraminic acid methylester (8). Removing of the isopropylidene group gives the alpha-methylketoside of 4-epi-N-acetylneuraminic acid alpha-methylketoside (10). On the other hand compound 5 was turned into the 4,8,9-tri-O-t-butyldimethylsilylderivative 11 a from which the corresponding 7-oxo-compound 12 by oxidation with RuO4 derives. The reduction of 12 with BH3 - NH3 yielded a 1:1 mixture of the starting material 11 a and the desired 7-epi-derivative 13 a which gives either via the purified peracetylated alpha-methylketosid of 7-epi-N-acetylneuraminic acid methylester (14) or a direct saponification the sodium salt of 7-epi-N-acetylneuraminic acid-alpha-methylketoside (15).Applying the Konigs-Knorr procedure to the peracetylated 8-epi-N-acetylneuraminic acid methylester (16) gives rise to the formation of a 1:1 mixture of the corresponding alpha- and beta-methylketosides 17 and 18 besides traces of the corresponding 2,3-dideoxy-2,3-dideohydro-sialic acid derivative 19. After chromatographic separation of 17 further saponification leads to the sodium salt of 8-epi-N-acetylneuraminic acid-alpha-methylketoside (20). In an analogous procedure the sodium salt of 7,8-di-epi-N-acetylneuraminic acid-alpha-methylketoside (25) was prepared starting from the peracetylated 7,8-di-epi-N-acetylneuraminic acid methylester (21), whereby a mixture of the alpha- and beta-methylketosides 22 and 23 was formed in a ratio 95:5 besides traces of the peracetylated 2,3-dideoxy-2,3-didehydrosialic acid methylester (24).

  DOI：

  10.1007/bf00811116
• 作为产物：
  描述：

  methyl (methyl 5-acetamido-3,5-dideoxy-8,9-O-isopropylidene-D-glycero-α-D-galacto-2-nonulopyrasidonate) 在 ammonia borane 、 四氧化钌 、 溶剂黄146 作用下， 以 甲醇 、 氯仿 为溶剂， 反应 1.5h， 生成 Methyl-(methyl-5-acetamido-3,5-dideoxy-D-glycero-α-D-talo-nonulopyranosid)onat
  参考文献：
  名称：

  Strukturelle Abwandlungen an N-Acetylneuramins�ure, 25. Mitt.: Synthese von Methyl-2-?-glycosiden von 4-epi-, 7-epi-, 8-epi- und 7,8-bis-epi-N-Acetylneuramins�ure

  摘要：

  The alpha-methylketoside of N-acetylneuraminic acid methylester (4) is transformed via the deacetylated compound 5 into the 9,8-O-isopropylidenderivative 6 which could be oxidized regioselectivity by RuO4 to the corresponding 4-oxo-sialic acid analogue 7. Reduction with the borane-ammonia complex produces a 1:1 mixture of 6 and the desired alpha-methylketoside of 9,8-O-isopropyliden-4-epi-N-acetyl-neuraminic acid methylester (8). Removing of the isopropylidene group gives the alpha-methylketoside of 4-epi-N-acetylneuraminic acid alpha-methylketoside (10). On the other hand compound 5 was turned into the 4,8,9-tri-O-t-butyldimethylsilylderivative 11 a from which the corresponding 7-oxo-compound 12 by oxidation with RuO4 derives. The reduction of 12 with BH3 - NH3 yielded a 1:1 mixture of the starting material 11 a and the desired 7-epi-derivative 13 a which gives either via the purified peracetylated alpha-methylketosid of 7-epi-N-acetylneuraminic acid methylester (14) or a direct saponification the sodium salt of 7-epi-N-acetylneuraminic acid-alpha-methylketoside (15).Applying the Konigs-Knorr procedure to the peracetylated 8-epi-N-acetylneuraminic acid methylester (16) gives rise to the formation of a 1:1 mixture of the corresponding alpha- and beta-methylketosides 17 and 18 besides traces of the corresponding 2,3-dideoxy-2,3-dideohydro-sialic acid derivative 19. After chromatographic separation of 17 further saponification leads to the sodium salt of 8-epi-N-acetylneuraminic acid-alpha-methylketoside (20). In an analogous procedure the sodium salt of 7,8-di-epi-N-acetylneuraminic acid-alpha-methylketoside (25) was prepared starting from the peracetylated 7,8-di-epi-N-acetylneuraminic acid methylester (21), whereby a mixture of the alpha- and beta-methylketosides 22 and 23 was formed in a ratio 95:5 besides traces of the peracetylated 2,3-dideoxy-2,3-didehydrosialic acid methylester (24).

  DOI：

  10.1007/bf00811116

文献信息

• Strukturelle Abwandlungen an N-Acetylneuramins�ure, 25. Mitt.: Synthese von Methyl-2-?-glycosiden von 4-epi-, 7-epi-, 8-epi- und 7,8-bis-epi-N-Acetylneuramins�ure
  作者：B. P. Bandgar、E. Zbiral

  DOI：10.1007/bf00811116

  日期：1991.12

  The alpha-methylketoside of N-acetylneuraminic acid methylester (4) is transformed via the deacetylated compound 5 into the 9,8-O-isopropylidenderivative 6 which could be oxidized regioselectivity by RuO4 to the corresponding 4-oxo-sialic acid analogue 7. Reduction with the borane-ammonia complex produces a 1:1 mixture of 6 and the desired alpha-methylketoside of 9,8-O-isopropyliden-4-epi-N-acetyl-neuraminic acid methylester (8). Removing of the isopropylidene group gives the alpha-methylketoside of 4-epi-N-acetylneuraminic acid alpha-methylketoside (10). On the other hand compound 5 was turned into the 4,8,9-tri-O-t-butyldimethylsilylderivative 11 a from which the corresponding 7-oxo-compound 12 by oxidation with RuO4 derives. The reduction of 12 with BH3 - NH3 yielded a 1:1 mixture of the starting material 11 a and the desired 7-epi-derivative 13 a which gives either via the purified peracetylated alpha-methylketosid of 7-epi-N-acetylneuraminic acid methylester (14) or a direct saponification the sodium salt of 7-epi-N-acetylneuraminic acid-alpha-methylketoside (15).Applying the Konigs-Knorr procedure to the peracetylated 8-epi-N-acetylneuraminic acid methylester (16) gives rise to the formation of a 1:1 mixture of the corresponding alpha- and beta-methylketosides 17 and 18 besides traces of the corresponding 2,3-dideoxy-2,3-dideohydro-sialic acid derivative 19. After chromatographic separation of 17 further saponification leads to the sodium salt of 8-epi-N-acetylneuraminic acid-alpha-methylketoside (20). In an analogous procedure the sodium salt of 7,8-di-epi-N-acetylneuraminic acid-alpha-methylketoside (25) was prepared starting from the peracetylated 7,8-di-epi-N-acetylneuraminic acid methylester (21), whereby a mixture of the alpha- and beta-methylketosides 22 and 23 was formed in a ratio 95:5 besides traces of the peracetylated 2,3-dideoxy-2,3-didehydrosialic acid methylester (24).