2-((3aS,5R,6R,6aS)-2,2-Dimethyl-5-phosphonooxymethyl-tetrahydro-furo[2,3-d][1,3]dioxol-6-yloxy)-acrylic acid methyl ester | 1054615-20-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-((3aS,5R,6R,6aS)-2,2-Dimethyl-5-phosphonooxymethyl-tetrahydro-furo[2,3-d][1,3]dioxol-6-yloxy)-acrylic acid methyl ester
• 英文别名: methyl 2-[[(3aS,5R,6R,6aS)-2,2-dimethyl-5-(phosphonooxymethyl)-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-6-yl]oxy]prop-2-enoate
• CAS: 1054615-20-1
• 化学式: C₁₂H₁₉O₁₀P
• 分子量: 354.251
• InChiKey: UEEMXNMWRCPCGH-REIXXSIJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.7
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  130
• 氢给体数：
  2
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  2-((3aS,5R,6R,6aS)-2,2-Dimethyl-5-phosphonooxymethyl-tetrahydro-furo[2,3-d][1,3]dioxol-6-yloxy)-acrylic acid methyl ester 在 Dowex 50W (H⁺) 作用下， 以 重水 为溶剂， 反应 24.0h， 生成 2-((2R,3S,4S)-4,5-Dihydroxy-2-phosphonooxymethyl-tetrahydro-furan-3-yloxy)-acrylic acid methyl ester
  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
• 作为产物：
  描述：

  1,2-O-(1-isopropylidene)-β-D-arabinofuranose 在 吡啶 、 dirhodium tetraacetate 、 溶剂黄146 、 三乙胺 、 锌 作用下， 以 甲醇 、 二氯甲烷 、 二甲基亚砜 、 苯 为溶剂， 反应 41.0h， 生成 2-((3aS,5R,6R,6aS)-2,2-Dimethyl-5-phosphonooxymethyl-tetrahydro-furo[2,3-d][1,3]dioxol-6-yloxy)-acrylic acid methyl ester
  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