methyl (4,5,7,8,9-penta-O-acetyl-2-(dibutylphosphoryl)-3-deoxy-D-glycero-β-D-galacto-non-2-ulopyranoside)onate | 1415022-21-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (4,5,7,8,9-penta-O-acetyl-2-(dibutylphosphoryl)-3-deoxy-D-glycero-β-D-galacto-non-2-ulopyranoside)onate
• 英文别名: dibutyl [methyl (4,5,7,8,9-penta-O-acetyl-3-deoxy-D-glycero-β-D-galacto-non-2-ulopyranosyl)onate]phosphate；methyl (2R,4S,5R,6R)-4,5-diacetyloxy-2-[dibutoxy(oxido)phosphaniumyl]oxy-6-[(1R,2R)-1,2,3-triacetyloxypropyl]oxane-2-carboxylate
• CAS: 1415022-21-7
• 化学式: C₂₈H₄₅O₁₇P
• 分子量: 684.629
• InChiKey: UEKRGTWEFVOXDD-IHDDDBKGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  46
• 可旋转键数：
  25
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  218
• 氢给体数：
  0
• 氢受体数：
  17

反应信息

• 作为反应物：
  描述：

  methyl (4,5,7,8,9-penta-O-acetyl-2-(dibutylphosphoryl)-3-deoxy-D-glycero-β-D-galacto-non-2-ulopyranoside)onate 、 烯丙基三丁基锡 在 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 以52%的产率得到methyl 2-C-allyl-4,5,7,8,9-penta-O-acetyl-2,6-anhydro-3,5-deoxy-D-glycero-α-D-galacto-nononate
  参考文献：
  名称：

  Influence of protecting groups on O- and C-glycosylation with neuraminyl and ulosonyl dibutylphosphates

  摘要：

  The adamantanyl thioglycosides of 5-isothiocyano and 5-azido 5-desamino-4,7,8,9-tetra-O-acetylneuraminic acid methyl ester were converted into the corresponding dibutyl phosphates, which proved to be excellent alpha-selective donors for O-sialidation with a range of typical acceptors, and good donors for reaction with allyltributylstannane, albeit without significant anomeric selectivity. In the KDN series the dibuylphosphate derived from a donor carrying a 4,5-cyclic carbonate protecting group afforded the corresponding C-glycoside with excellent alpha-selectivity on activation in the presence of allyltributylstannane, whereas the corresponding donor carrying acetate esters at the 4and 5-positions was unselective. Overall, it is revealed that while the strongly electron-withdrawing isothiocyanato and azido groups are sufficient to promote highly alpha-selective O-sialidation, they are inadequate when faced with less reactive nucleophiles when mixtures of anomers are obtained.

  DOI：

  10.1016/j.carres.2020.108100
• 作为产物：
  描述：

  methyl (1-adamantanyl-4,5,7,8,9-penta-O-acetyl-3-deoxy-β-D-glycero-D-galacto-2-thiononulopyranoside)onate 、 磷酸二丁酯 在 N-碘代丁二酰亚胺 、 三氟甲磺酸 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 0.5h， 以72%的产率得到methyl (4,5,7,8,9-penta-O-acetyl-2-(dibutylphosphoryl)-3-deoxy-D-glycero-β-D-galacto-non-2-ulopyranoside)onate
  参考文献：
  名称：

  Influence of protecting groups on O- and C-glycosylation with neuraminyl and ulosonyl dibutylphosphates

  摘要：

  The adamantanyl thioglycosides of 5-isothiocyano and 5-azido 5-desamino-4,7,8,9-tetra-O-acetylneuraminic acid methyl ester were converted into the corresponding dibutyl phosphates, which proved to be excellent alpha-selective donors for O-sialidation with a range of typical acceptors, and good donors for reaction with allyltributylstannane, albeit without significant anomeric selectivity. In the KDN series the dibuylphosphate derived from a donor carrying a 4,5-cyclic carbonate protecting group afforded the corresponding C-glycoside with excellent alpha-selectivity on activation in the presence of allyltributylstannane, whereas the corresponding donor carrying acetate esters at the 4and 5-positions was unselective. Overall, it is revealed that while the strongly electron-withdrawing isothiocyanato and azido groups are sufficient to promote highly alpha-selective O-sialidation, they are inadequate when faced with less reactive nucleophiles when mixtures of anomers are obtained.

  DOI：

  10.1016/j.carres.2020.108100

文献信息

• Dissecting the Influence of Oxazolidinones and Cyclic Carbonates in Sialic Acid Chemistry
  作者：Pavan K. Kancharla、Chandrasekhar Navuluri、David Crich

  DOI：10.1002/anie.201204400

  日期：2012.10.29

  At a moment′s notice: Thermal equilibration of 1 and mass spectral analysis of sialyl phosphates suggest that the 4O,5N‐oxazolidinone and the 4,5‐O‐carbonate systems influence the anomeric effect and the mechanisms of sialidation by virtue of their dipole moment in the mean plane of the pyranose ring. The electron‐withdrawing effect destabilizes 2 and promotes associative glycosylation mechanisms.

  即时通知: 1 的热平衡和磷酸唾液酸的质谱分析表明 4 O ,5 N-恶唑烷酮和 4,5- O-碳酸酯系统通过以下方式影响异头效应和唾液酸化机制它们在吡喃糖环的平均平面上的偶极矩。吸电子效应使2不稳定并促进缔合糖基化机制。TEMPO=2,2,6,6-四甲基哌啶N-氧化物。