diethyl 2-[(E)-hept-1-enyl]propanedioate | 138435-97-9

• 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: diethyl 2-[(E)-hept-1-enyl]propanedioate
• CAS: 138435-97-9
• 化学式: C₁₄H₂₄O₄
• 分子量: 256.342
• InChiKey: LGEDAOWUHAGSQJ-ZHACJKMWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.87
• 重原子数：
  18.0
• 可旋转键数：
  9.0
• 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

• 作为反应物：
  描述：

  diethyl 2-[(E)-hept-1-enyl]propanedioate 在 palladium on activated charcoal 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 氢气 、 三乙胺 作用下， 以 乙醚 、 乙醇 、 二氯甲烷 、 水 、 异丙醇 为溶剂， 反应 25.67h， 生成 Acetic acid (R)-2-hydroxymethyl-nonyl ester
  参考文献：
  名称：

  Chemoenzymic preparation of asymmetrized tris(hydroxymethyl)methane (THYM*) and of asymmetrized bis(hydroxymethyl)acetaldehyde (BHYMA*) as new highly versatile chiral building blocks

  摘要：

  A series of asymmetrized tris(hydroxymethyl)methanes 2 and bis(hydroxymethyl)acetaldehydes 3 have been prepared in both enantiomeric forms through a chemoenzymatic methodology. The key step is the highly enantioselective PPL-catalyzed monohydrolysis of 2(E)-alkenyl-1,3-diacetoxypropanes 25-27. A careful study on the effect of unsaturations adjacent to the prochiral center in a series of 2-substituted 1,3-diacetoxypropanes has confirmed the suggested beneficial effect of a pi-system in that position but has also unveiled an unprecedented dramatic effect of double-bond configuration on enantioselectivity. A new empirical model for the interpretation of these and other results, based both on polarity and steric arguments, is proposed. This study provides a general protocol for the efficient synthesis of asymmetrized 1,3-propanediols bearing in position 2 saturated or unsaturated carbon chains.

  DOI：

  10.1021/jo00031a039
• 作为产物：
  描述：

  1,3-diethyl 2-heptylidenepropanedioate 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 正己烷 为溶剂， 以72%的产率得到diethyl 2-[(E)-hept-1-enyl]propanedioate
  参考文献：
  名称：

  Chemoenzymic preparation of asymmetrized tris(hydroxymethyl)methane (THYM*) and of asymmetrized bis(hydroxymethyl)acetaldehyde (BHYMA*) as new highly versatile chiral building blocks

  摘要：

  A series of asymmetrized tris(hydroxymethyl)methanes 2 and bis(hydroxymethyl)acetaldehydes 3 have been prepared in both enantiomeric forms through a chemoenzymatic methodology. The key step is the highly enantioselective PPL-catalyzed monohydrolysis of 2(E)-alkenyl-1,3-diacetoxypropanes 25-27. A careful study on the effect of unsaturations adjacent to the prochiral center in a series of 2-substituted 1,3-diacetoxypropanes has confirmed the suggested beneficial effect of a pi-system in that position but has also unveiled an unprecedented dramatic effect of double-bond configuration on enantioselectivity. A new empirical model for the interpretation of these and other results, based both on polarity and steric arguments, is proposed. This study provides a general protocol for the efficient synthesis of asymmetrized 1,3-propanediols bearing in position 2 saturated or unsaturated carbon chains.

  DOI：

  10.1021/jo00031a039