(3Z,5E,11E)-dimethyl-8,8-bis(methoxycarbonyl)-14-chloro-12-methyl-13-hydroxytetradeca-3,5,11-trienedicarboxylate | 290292-39-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (3Z,5E,11E)-dimethyl-8,8-bis(methoxycarbonyl)-14-chloro-12-methyl-13-hydroxytetradeca-3,5,11-trienedicarboxylate
• 英文别名: tetramethyl (3Z,5E,11E)-14-chloro-13-hydroxy-12-methyltetradeca-3,5,11-triene-1,1,8,8-tetracarboxylate
• CAS: 290292-39-6
• 化学式: C₂₃H₃₃ClO₉
• 分子量: 488.963
• InChiKey: RHWWNADMVYQXAL-KLTFWYMASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  33.0
• 可旋转键数：
  14.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  125.43
• 氢给体数：
  1.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  (3Z,5E,11E)-dimethyl-8,8-bis(methoxycarbonyl)-14-chloro-12-methyl-13-hydroxytetradeca-3,5,11-trienedicarboxylate 在 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 为溶剂， 反应 0.08h， 以96%的产率得到(3Z,5E,11E)-dimethyl-8,8-bis(methoxycarbonyl)-14-chloro-12-methyl-13-oxotetradeca-3,5,11-trienedicarboxylate
  参考文献：
  名称：

  Transannular Diels–Alder Studies of 14-Membered cis – trans – trans Macrocyclic Trienes Having Allylic Ether or Enone Dienophile

  摘要：

  Highly convergent, malonate alkylation based syntheses of the model macrocycles and their title investigations are reported. In the allylic ether dienophile case, a preference for tricycles with equatorial ether position was found at the transition state level. Ab initio calculations also show that the origin of this preference is not only steric but stereoelectronic as well. The enone dienophile case indicates that when the enone system is not totally twisted out of planarity by the macrocyclic environment, the Diels-Alder reaction follows the usual trend in terms of dienophile activation. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)00455-5
• 作为产物：
  描述：

  (E)-ethyl-2-methyl-5-tetrahydropyranyloxy-2-pentenoate 在 2,6-二甲基吡啶 、 正丁基锂 、 草酰氯 、 六氯丙酮 、 四丁基氟化铵 、 4-甲基苯磺酸吡啶 、 potassium hydride 、 sodium hydride 、 二异丁基氢化铝 、 对甲苯磺酸 、 二甲基亚砜 、 三乙胺 、 三苯基膦 、 potassium iodide 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 28.5h， 生成 (3Z,5E,11E)-dimethyl-8,8-bis(methoxycarbonyl)-14-chloro-12-methyl-13-hydroxytetradeca-3,5,11-trienedicarboxylate
  参考文献：
  名称：

  Transannular Diels–Alder Studies of 14-Membered cis – trans – trans Macrocyclic Trienes Having Allylic Ether or Enone Dienophile

  摘要：

  Highly convergent, malonate alkylation based syntheses of the model macrocycles and their title investigations are reported. In the allylic ether dienophile case, a preference for tricycles with equatorial ether position was found at the transition state level. Ab initio calculations also show that the origin of this preference is not only steric but stereoelectronic as well. The enone dienophile case indicates that when the enone system is not totally twisted out of planarity by the macrocyclic environment, the Diels-Alder reaction follows the usual trend in terms of dienophile activation. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)00455-5