Methyl-(methyl-5-acetamido-4,8,9-tri-O-t-butyldimethylsilyl-3,5-dideoxy-D-glycero-α-D-galacto-2,7-di-nonulopyranosid)onat | 111410-64-1

• 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-4,8,9-tri-O-t-butyldimethylsilyl-3,5-dideoxy-D-glycero-α-D-galacto-2,7-di-nonulopyranosid)onat
• 英文别名: methyl (2R,4S,5S,6R)-5-acetamido-6-[(2R)-2,3-bis[[tert-butyl(dimethyl)silyl]oxy]propanoyl]-4-[tert-butyl(dimethyl)silyl]oxy-2-methoxyoxane-2-carboxylate
• CAS: 111410-64-1；140195-56-8
• 化学式: C₃₁H₆₃NO₉Si₃
• 分子量: 678.099
• InChiKey: KZZIYCXINLAEGV-XNPNDBCHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.17
• 重原子数：
  44.0
• 可旋转键数：
  12.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  118.62
• 氢给体数：
  1.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  Methyl-(methyl-5-acetamido-4,8,9-tri-O-t-butyldimethylsilyl-3,5-dideoxy-D-glycero-α-D-galacto-2,7-di-nonulopyranosid)onat 在 吡啶 、 4-二甲氨基吡啶 、 硼烷铵络合物 、 溶剂黄146 作用下， 以 甲醇 为溶剂， 反应 11.5h， 生成 Methyl-(methyl-5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-α-L-altro-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：

  Methyl-(methyl-5-acetamido-4,8,9-tri-O-t-butyldimethylsilyl-7-O-acetyl-3,5-dideoxy-D-glycero-α-D-galacto-2-nonulopyranosid)onat 在 四氧化钌 作用下， 以 氯仿 为溶剂， 反应 1.0h， 以91.5%的产率得到Methyl-(methyl-5-acetamido-4,8,9-tri-O-t-butyldimethylsilyl-3,5-dideoxy-D-glycero-α-D-galacto-2,7-di-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