Methyl-5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-L-glycero-α-L-altro-2-nonulopyranosidonsaeuremethylester | 41521-03-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Methyl-5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-L-glycero-α-L-altro-2-nonulopyranosidonsaeuremethylester
• 英文别名: methyl [methyl 4,7,8,9-tetra-O-acetyl-5-acetamido-3,5-dideoxy-α-D-glycero-D-galacto-non-2-ulopyranoside]onate；Methyl-4,7,8,9-tetra-O-acetyl-5-acetylamino-3,5-didesoxy-β-D-glycero-L-altro-2-nonulopyranosidonsaeuremethylester；Methyl-(methyl-5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-α-L-altro-2-nonulopyranosid)onat；Methyl-4,7,8,9-tetra-O-acetyl-5-acetylamino-3,5-didesoxy-β-L-glycero-D-galacto-2-nonulopyranosidonsaeuremethylester；(1S,2R)-1-((2R,3R,4S,6S)-3-acetamido-4-acetoxy-6-methoxy-6-(methoxycarbonyl)tetrahydro-2H-pyran-2-yl)propane-1,2,3-triyl triacetate；Methyl-4,7,8,9-tetra-O-acetyl-5-acetylamino-3,5-didesoxy-β-L-glycero-L-altro-2-nonulopyranosidonsaeuremethylester；methyl α-glycoside of methyl 5-N-acetyl-4,7,8,9-tetra-O-acetyl-D-neuraminate；Methyl-5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-L-glycero-α-D-galacto-2-nonulopyranosidonsaeuremethylester
• CAS: 41521-03-3；56323-64-9；73208-80-7；88547-02-8；99395-95-6；99395-96-7；99395-97-8；140385-82-6；140385-83-7；140385-84-8
• 化学式: C₂₁H₃₁NO₁₃
• 分子量: 505.476
• InChiKey: BDVAGIAWBFWKLD-COXOLSDPSA-N

物化性质

• 沸点：
  593.7±50.0 °C(Predicted)
• 密度：
  1.29±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.85
• 重原子数：
  35.0
• 可旋转键数：
  10.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  179.06
• 氢给体数：
  1.0
• 氢受体数：
  13.0

反应信息

• 作为反应物：
  描述：

  Methyl-5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-L-glycero-α-L-altro-2-nonulopyranosidonsaeuremethylester 在 水 、 sodium methylate 作用下， 生成 Natrium-(methyl-5-acetamido-3,5-dideoxy-L-glycero-α-D-galacto-2-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
• 作为产物：
  描述：

  N-Acetylneuraminic Acid Methyl Ester 2,4,7,8,9-Pentaacetate 在 盐酸 、 乙酰氯 、 silver carbonate 作用下， 以 乙醚 为溶剂， 反应 19.0h， 生成 Methyl-5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-L-glycero-α-L-altro-2-nonulopyranosidonsaeuremethylester
  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

• Studies on sialic acids I. Determination of anomeric configuration of neuraminic acid derivatives by circular dichroism
  作者：Haruo Ogura、Kimio Furuhata

  DOI：10.1016/s0040-4039(01)82928-2

  日期：1981.1

  CD spectra were recorded for methyl α- and β-glycosides of -neuraminic acid, and the band at the wave-length lower than 200 nm was attributed to the acetamido group. The Cotton effect at higher wave-length around 220 nm arose from the n-πx transition of the carboxyl group. Thus α-linked glycosides snowed a negative band, while β-glycosides gave arise to a positive band.

  记录了CD-神经氨酸的甲基α-和β-糖苷的光谱，并且波长小于200nm的谱带归因于乙酰胺基。在约220纳米以上的波长的Cotton效应从n-π出现X的羧基的转变。因此，α-连接的糖苷下雪为负带，而给出的β-糖苷出现正带。