methyl (1S,3R,4R,5R)-5-hydroxy-3-[(1R)-1-hydroxy-2-(4-methylphenyl)sulfonyloxyethyl]-2,7-dioxabicyclo[2.2.1]heptane-1-carboxylate | 178426-28-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (1S,3R,4R,5R)-5-hydroxy-3-[(1R)-1-hydroxy-2-(4-methylphenyl)sulfonyloxyethyl]-2,7-dioxabicyclo[2.2.1]heptane-1-carboxylate
• CAS: 178426-28-3
• 化学式: C₁₆H₂₀O₉S
• 分子量: 388.395
• InChiKey: PBBNECRBRVOJHV-PAURTPPISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  26
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  137
• 氢给体数：
  2
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  methyl (1S,3R,4R,5R)-5-hydroxy-3-[(1R)-1-hydroxy-2-(4-methylphenyl)sulfonyloxyethyl]-2,7-dioxabicyclo[2.2.1]heptane-1-carboxylate 在 四氯化锡 作用下， 以 二氯甲烷 为溶剂， 生成 methyl (4R,5R)-5-[(1R,2R)-1,2-dihydroxy-3-(4-methylphenyl)sulfonyloxypropyl]-2,4-dihydroxyoxolane-2-carboxylate
  参考文献：
  名称：

  通过类似于Kdo8P合成酶建议机制的Kdo结构立体选择性构建的新模型

  摘要：

  使用与针对酶Kdo8P合酶建议的机制相似的机制证明了Kdo结构的立体特异性化学合成。在12个化学步骤中合成了D-（-）-阿拉伯糖（化合物3）的衍生物，其中烯醇丙酮酸部分连接在C-3羟基上，并在路易斯酸条件下检查了烯醇丙酮酸的分子内缩合和醛功能。

  DOI：

  10.1016/0040-4039(96)00608-9
• 作为产物：
  描述：

  methyl 2-[(2R,3S,4S)-4,5-dihydroxy-2-[(4-methylphenyl)sulfonyloxymethyl]oxolan-3-yl]oxyprop-2-enoate 在 四氯化锡 作用下， 以 二氯甲烷 为溶剂， 反应 5.0h， 以68.2%的产率得到methyl (1S,3R,4R,5R)-5-hydroxy-3-[(1R)-1-hydroxy-2-(4-methylphenyl)sulfonyloxyethyl]-2,7-dioxabicyclo[2.2.1]heptane-1-carboxylate
  参考文献：
  名称：

  First Nonenzymatic Synthesis of Kdo8P through a Mechanism Similar to That Suggested for the Enzyme Kdo8P Synthase

  摘要：

  The mechanism of Kdo8P synthase, the enzyme that catalyzes the unusual condensation of D-arabinose 5-phosphate (A5P) with phosphoenolpyruvate (PEP) to form Kdo8P, remains a fascinating subject for bioorganic research. This paper describes the synthesis of two intramolecular models (1 and 2) bearing an enolpyruvate moiety at C-3 of the arabinose fraction. This means that their open-chain aldehyde forms closely mimic the proposed. situation, whereby two substrates A5P and PEP evolve into a ternary complex with the synthase. Examination of 1 (in organic solvent) and 2 (in a water solution) under Lewis acid conditions establishes that they both undergo highly stereospecific intramolecular condensation of the enolpyruvate double bond with the carbonyl of sugar. This results in the required Kdo structure possessing the desired stereochemistry. Mechanistic studies suggest that the observed intramolecular condensation process takes place via a stepwise mechanism involving the formation of a transient oxocarbenium ion intermediate. The results obtained, uniquely demonstrate enzyme-like chemistry in the stereospecific synthesis of the Kdo system. Further investigation is certainly warranted, in order to facilitate the construction of other 3-deoxy-2-ulosonoc acids and sialic acids on the basis of the same general model. This is illustrated here in the case of Kdo. Furthermore, the results support the validity of the mechanism suggested for the Kdo8P synthase action, in particular, the possible role. of the enzyme in the catalysis of the initial condensation step.

  DOI：

  10.1021/jo961929y

文献信息

• First Nonenzymatic Synthesis of Kdo8P through a Mechanism Similar to That Suggested for the Enzyme Kdo8P Synthase
  作者：Shoucheng Du、Dorit Plat、Valery Belakhov、Timor Baasov

  DOI：10.1021/jo961929y

  日期：1997.2.1

  The mechanism of Kdo8P synthase, the enzyme that catalyzes the unusual condensation of D-arabinose 5-phosphate (A5P) with phosphoenolpyruvate (PEP) to form Kdo8P, remains a fascinating subject for bioorganic research. This paper describes the synthesis of two intramolecular models (1 and 2) bearing an enolpyruvate moiety at C-3 of the arabinose fraction. This means that their open-chain aldehyde forms closely mimic the proposed. situation, whereby two substrates A5P and PEP evolve into a ternary complex with the synthase. Examination of 1 (in organic solvent) and 2 (in a water solution) under Lewis acid conditions establishes that they both undergo highly stereospecific intramolecular condensation of the enolpyruvate double bond with the carbonyl of sugar. This results in the required Kdo structure possessing the desired stereochemistry. Mechanistic studies suggest that the observed intramolecular condensation process takes place via a stepwise mechanism involving the formation of a transient oxocarbenium ion intermediate. The results obtained, uniquely demonstrate enzyme-like chemistry in the stereospecific synthesis of the Kdo system. Further investigation is certainly warranted, in order to facilitate the construction of other 3-deoxy-2-ulosonoc acids and sialic acids on the basis of the same general model. This is illustrated here in the case of Kdo. Furthermore, the results support the validity of the mechanism suggested for the Kdo8P synthase action, in particular, the possible role. of the enzyme in the catalysis of the initial condensation step.
• A new model for the stereoselective construction of the Kdo structure through a mechanism similar to that suggested for the enzyme Kdo8P synthase
  作者：Shoucheng Du、Dorit Plat、Timor Baasov

  DOI：10.1016/0040-4039(96)00608-9

  日期：1996.5

  Stereospecific chemical synthesis of the Kdo structure was demonstrated using a mechanism similar to that suggested for the enzyme Kdo8P synthase. The derivative of D-(−)-arabinose (compound 3), in which the enolpyruvate moiety is attached at C-3 hydroxyl, was synthesized in 12 chemical steps and an intramolecular condensation of enolpyruvate and aldehyde functions was examined, under Lewis acid conditions

  使用与针对酶Kdo8P合酶建议的机制相似的机制证明了Kdo结构的立体特异性化学合成。在12个化学步骤中合成了D-（-）-阿拉伯糖（化合物3）的衍生物，其中烯醇丙酮酸部分连接在C-3羟基上，并在路易斯酸条件下检查了烯醇丙酮酸的分子内缩合和醛功能。