ethyl 3-heptenoate | 21994-75-2

• 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-heptenoate
• 英文别名: Hepten-(3)-saeureethylester；3-Heptenoic acid, ethyl ester；ethyl hept-3-enoate
• CAS: 21994-75-2
• 化学式: C₉H₁₆O₂
• 分子量: 156.225
• InChiKey: MOTXKEQQXJIDHO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  11
• 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：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  3-己烯酸乙酯 、 乙醇 、 一氧化碳 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex N,N-二异丙基乙胺 、 三苯基膦 、 sodium bromide 作用下， 50.0 ℃ 、3.04 MPa 条件下， 反应 20.0h， 以78%的产率得到ethyl 3-heptenoate
  参考文献：
  名称：

  Palladium(0)-catalyzed alkoxycarbonylation of allyl phosphates and acetates

  摘要：

  Palladium-catalyzed alkoxycarbonylation of allyl phosphates under CO (1 atm) at 50-degrees-C proceeds highly efficiently to give the corresponding beta,gamma-unsaturated esters. The carbonylation of geranyl phosphate ((E)-11) under CO (1 atm) at 50-degrees-C gave ethyl ester of homogeranic acid ((E)-12) stereoselectively. The carbonylation takes place at the least substituted allylic positions with inversion of configuration. Typically, the methoxycarbonylation of cis-5-(methoxycarbonyl)-2-cyclohexen-1-yl phosphate (cis-16) gave trans-dimethyl 2-cyclohexene-1,5-dicarboxylate (trans-17) selectively. Alkoxycarbonylation of allyl acetates is performed for the first time in the presence of a catalytic amount of bromide ion. The reaction can be rationalized by assuming the mechanism which involves oxidative addition of palladium(0) species to allyl acetates to give pi-allylpalladium acetate, fast ligand exchange of the acetate with bromide, insertion of carbon monoxide to give acylpalladium species, and alkoxylation.

  DOI：

  10.1021/jo00058a040

文献信息

• Fluorinated allylic alcohols as building blocks
  作者：Thomas Allmendinger、Christoph Angst、Heinrich Karfunkel

  DOI：10.1016/0022-1139(94)00415-c

  日期：1995.6

  A theoretical study on the carbocationic reactivity of 2-fluoroallylic alcohols and derivatives explains some experimental findings. An outline is also given of synthetic approaches towards fluoroallylic amines and more complex carbon skeletons starting with fluoroallylic alcohols.
• Palladium(0)-catalyzed alkoxycarbonylation of allyl phosphates and acetates
  作者：Shunichi Murahashi、Yasushi Imada、Yuki Taniguchi、Shinya Higashiura

  DOI：10.1021/jo00058a040

  日期：1993.3

  Palladium-catalyzed alkoxycarbonylation of allyl phosphates under CO (1 atm) at 50-degrees-C proceeds highly efficiently to give the corresponding beta,gamma-unsaturated esters. The carbonylation of geranyl phosphate ((E)-11) under CO (1 atm) at 50-degrees-C gave ethyl ester of homogeranic acid ((E)-12) stereoselectively. The carbonylation takes place at the least substituted allylic positions with inversion of configuration. Typically, the methoxycarbonylation of cis-5-(methoxycarbonyl)-2-cyclohexen-1-yl phosphate (cis-16) gave trans-dimethyl 2-cyclohexene-1,5-dicarboxylate (trans-17) selectively. Alkoxycarbonylation of allyl acetates is performed for the first time in the presence of a catalytic amount of bromide ion. The reaction can be rationalized by assuming the mechanism which involves oxidative addition of palladium(0) species to allyl acetates to give pi-allylpalladium acetate, fast ligand exchange of the acetate with bromide, insertion of carbon monoxide to give acylpalladium species, and alkoxylation.