Ethyl 3-<<(tert-butyldimethylsilyl)oxy>methyl>-4-oxo-2-pentenoate | 137570-88-8

• 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 3-<<(tert-butyldimethylsilyl)oxy>methyl>-4-oxo-2-pentenoate
• CAS: 137570-88-8；137570-89-9
• 化学式: C₁₄H₂₆O₄Si
• 分子量: 286.444
• InChiKey: ULMWVNHLAIYFPH-UHFFFAOYSA-N

物化性质

• 沸点：
  348.3±42.0 °C(Predicted)
• 密度：
  0.968±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.09
• 重原子数：
  19.0
• 可旋转键数：
  6.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为产物：
  描述：

  4-(tert-butyldimethylsilyloxy)-2-butyn-1-ol 、 2-Chloro-2-ethoxyvinyl 4-chlorophenyl sulfoxide 在 甲基锂 作用下， 生成 Ethyl 3-<<(tert-butyldimethylsilyl)oxy>methyl>-4-oxo-2-pentenoate
  参考文献：
  名称：

  One-flask, consecutive [3,3]- and [2,3]-sigmatropic rearrangements for conversions of propargylic alcohols into 2-carbon-extended 4-oxo-2-alkenoate esters. Use of a new 1-chloro-1-ethoxy-2-sulfinylethylene

  摘要：

  Seven differently substituted primary and secondary propargylic alcohols are shown to react with (arylsulfinyl) vinylic chloride 1a at 100-degrees-C for 1 h sequentially via a [3,3] sigmatropic rearrangement and then a [2,3] sigmatropic rearrangement to form 4-oxo-2-alkenoates 8a-8e and 9a and 9b in 52-80% yields. This one-flask, intramolecular carbon-carbon bond-forming process represents a simple and convenient method not only for regiospecific gamma-attachment onto a propargylic alcohol of a two-carbon (ethoxycarbonyl)methylene unit but also for alpha --> beta transposition of oxygen. The synthetic utility of this procedure is illustrated further by eqs 2 and 3 for preparation of regiospecifically functionalized carbocycles and heterocycles. Also, two different primary allenic allylic alcohols are shown to produce directly two-carbon extended 3-(hydroxyalkyl)-2,4-pentadienoates (E)-18 and the corresponding unsaturated lactones (Z)-18 in 37-41% yields.

  DOI：

  10.1021/jo00025a009