ethyl 2-diethylphosphono-2-(cyclohex-2-en-1-yloxy)acetate | 138090-71-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: ethyl 2-diethylphosphono-2-(cyclohex-2-en-1-yloxy)acetate
• 英文别名: ethyl 2-cyclohex-2-en-1-yloxy-2-diethoxyphosphorylacetate
• CAS: 138090-71-8；138090-72-9
• 化学式: C₁₄H₂₅O₆P
• 分子量: 320.323
• InChiKey: ZVWFPJRFDABUKT-UHFFFAOYSA-N

物化性质

• 沸点：
  425.8±45.0 °C(Predicted)
• 密度：
  1.13±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.27
• 重原子数：
  21.0
• 可旋转键数：
  9.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  71.06
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  ethyl 2-diethylphosphono-2-(cyclohex-2-en-1-yloxy)acetate 在 sodium hydroxide 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 168.0h， 生成 3-(1-Diethoxyphosphorylethenoxy)cyclohexene
  参考文献：
  名称：

  Phosphonate analogs of chorismic acid: synthesis and evaluation as mechanism-based inactivators of chorismate mutase

  摘要：

  The mechanism of chorismate mutase, the enzyme which catalyzes the Claisen arrangement of chorismic to prephenic acid, remains a fascinating area for bioorganic research. This paper describes the enantioselective synthesis of phosphonochorismic acids 3 and 4, two potential mechanism-based mutase inactivators, utilizing new transition-metal-catalyzed insertion reactions of tetraalkyl diazophosphonates. Models establish that such systems undergo smooth Claisen rearrangement and that the product acylphosphonates are good acylating agents for amines and alcohols. By contrast, thermolysis of phosphonochorismates 3 and 4 in the presence of enzyme led to p-hydroxybenzoic acid, with no trace of [3,3] rearrangement to the corresponding prephenates or phenylpyruvates. The half-life for elimination of 3 was 8.3 h (75-degrees-C, 2:1 CD3OD/D2O) while for 4 the half-life was 4.3 h. When tested over a wide range of concentrations against the E. coli chorismate mutases (so-called T- and P-proteins), neither 3 nor 4 interacted with the enzyme, either as a competitive inhibitor or as a substrate, perhaps reflecting the stringent demands of the rearrangment transition state. Earlier studies strongly suggest that the enol pyruvate carboxyl group is markedly tilted against the carbocyclic ring during [3,3] sigmatropy, and similar flattening of the tetrahedral phosphonate could create unfavorable steric as well as pi-pi interactions.

  DOI：

  10.1021/jo00027a034
• 作为产物：
  描述：

  ethyl 2-diazo-2-diethylphosphonoacetate 、 2-环己烯醇 在 rhodium acetate 作用下， 以 苯 为溶剂， 反应 4.0h， 生成 ethyl 2-diethylphosphono-2-(cyclohex-2-en-1-yloxy)acetate
  参考文献：
  名称：

  Brønsted Base Catalyzed [2,3]-Wittig/Phospha-Brook Tandem Rearrangement Sequence

  摘要：

  A Bronsted base catalyzed rearrangement reaction of 2-allyloxy-2-phosphonoacetate derivatives was developed. This reaction proceeded via a [2,3]-Wittig rearrangement followed by a phospha-Brook rearrangement. This is the first example of a catalytic [2,3]-Wittig rearrangement initiated by a Bronsted base.

  DOI：

  10.1021/ol402144q