1,3-丙二醇,2-(3-甲基-1-丁炔基)-,二乙酸酯 | 133490-85-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 中文名称: 1,3-丙二醇,2-(3-甲基-1-丁炔基)-,二乙酸酯
• 英文名称: 1-Acetoxy-2-(acetoxymethyl)-5-methyl-3-hexyne
• 英文别名: [2-(Acetyloxymethyl)-5-methylhex-3-ynyl] acetate
• CAS: 133490-85-4
• 化学式: C₁₂H₁₈O₄
• 分子量: 226.273
• InChiKey: KZWMLMJWKHXZMY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,3-丙二醇,2-(3-甲基-1-丁炔基)-,二乙酸酯 在 palladium, 5% on calcium carbonate, poisoned with lead 2,6-二甲基吡啶 、 氢气 作用下， 以 乙醇 为溶剂， 反应 5.0h， 以80%的产率得到(Z)-1-Acetoxy-2-(acetoxymethyl)-5-methyl-3-hexene
  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：

  3-甲基-1-丁炔 在 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 正丁基锂 、 三乙胺 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 6.0h， 生成 1,3-丙二醇,2-(3-甲基-1-丁炔基)-,二乙酸酯
  参考文献：
  名称：

  Enzymes in organic synthesis: remarkable influence of a π system on the enantioselectivity in PPL catalysed monohydrolysis of 2-substituted 1,3-diacetoxypropanes.

  摘要：

  DOI：

  10.1016/s0957-4166(00)82383-6

文献信息

• Enzymes in organic synthesis: remarkable influence of a π system on the enantioselectivity in PPL catalysed monohydrolysis of 2-substituted 1,3-diacetoxypropanes.
  作者：Giuseppe Guanti、Luca Banfi、Enrica Narisano

  DOI：10.1016/s0957-4166(00)82383-6

  日期：1990.1
• Chemoenzymic preparation of asymmetrized tris(hydroxymethyl)methane (THYM*) and of asymmetrized bis(hydroxymethyl)acetaldehyde (BHYMA*) as new highly versatile chiral building blocks
  作者：Giuseppe Guanti、Luca Banfi、Enrica Narisano

  DOI：10.1021/jo00031a039

  日期：1992.2

  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.