tert-butyl 7-chloro-4-methoxy-2(E)-heptenoate | 138542-14-0

• 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: tert-butyl 7-chloro-4-methoxy-2(E)-heptenoate
• 英文别名: tert-butyl (E)-7-chloro-4-methoxyhept-2-enoate
• CAS: 138542-14-0
• 化学式: C₁₂H₂₁ClO₃
• 分子量: 248.75
• InChiKey: QHSSFRKPLQMKRV-BQYQJAHWSA-N

物化性质

• 沸点：
  316.8±42.0 °C(Predicted)
• 密度：
  1.028±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.92
• 重原子数：
  16.0
• 可旋转键数：
  6.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  tert-butyl 7-chloro-4-methoxy-2(E)-heptenoate 在 sodium iodide 作用下， 以 丙酮 为溶剂， 反应 24.0h， 以68%的产率得到tert-butyl 7-iodo-4-methoxy-2(E)-heptenoate
  参考文献：
  名称：

  Stereochemistry of metal-halogen exchange-initiated intramolecular conjugate addition reactions in the construction of 5-membered carbocycles

  摘要：

  The stereochemistry of some lithium-iodine exchange-initiated cyclization reactions of model omega-iodo, gamma-substituted activated olefins has been studied. The stereoselectivities of these anionic cyclization reactions have been found to be a function of the olefin activator employed, reaction conditions, Michael acceptor olefin geometry, the nature of the gamma-substituent, and, in some cases, the presence of additives. Cyclization reactions of iodides possessing E olefin geometry give a moderate preference for trans cyclopentane formation while Z olefin geometry leads to extremely high (> 300:1) trans product selectivity. Cyclization reactions of E olefins under radical conditions were found to be slightly more trans-selective than those observed under anionic conditions although Z olefin geometry again promotes very high trans product selectivity. The presence of the allylic methoxyl group in (E)-7d leads to cis selectivity under both anionic and radical conditions. Intramolecular complexation involving the reactive carbon center and the methoxyl group is suggested in both modes as a possible explanation for this cis product selectivity.

  DOI：

  10.1021/jo00031a031
• 作为产物：
  描述：

  methyl 5-chloro-2-methoxypentanoate 在 sodium hydride 、 二异丁基氢化铝 作用下， 以 正己烷 、 甲苯 为溶剂， 反应 0.31h， 生成 tert-butyl 7-chloro-4-methoxy-2(E)-heptenoate
  参考文献：
  名称：

  Stereochemistry of metal-halogen exchange-initiated intramolecular conjugate addition reactions in the construction of 5-membered carbocycles

  摘要：

  The stereochemistry of some lithium-iodine exchange-initiated cyclization reactions of model omega-iodo, gamma-substituted activated olefins has been studied. The stereoselectivities of these anionic cyclization reactions have been found to be a function of the olefin activator employed, reaction conditions, Michael acceptor olefin geometry, the nature of the gamma-substituent, and, in some cases, the presence of additives. Cyclization reactions of iodides possessing E olefin geometry give a moderate preference for trans cyclopentane formation while Z olefin geometry leads to extremely high (> 300:1) trans product selectivity. Cyclization reactions of E olefins under radical conditions were found to be slightly more trans-selective than those observed under anionic conditions although Z olefin geometry again promotes very high trans product selectivity. The presence of the allylic methoxyl group in (E)-7d leads to cis selectivity under both anionic and radical conditions. Intramolecular complexation involving the reactive carbon center and the methoxyl group is suggested in both modes as a possible explanation for this cis product selectivity.

  DOI：

  10.1021/jo00031a031