(3E,5E,11Z)-tetramethyl 11-methylcyclotetradeca-3,5,11-triene-1,1,8,8-tetracarboxylate | 118089-46-6

• 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
• 英文名称: (3E,5E,11Z)-tetramethyl 11-methylcyclotetradeca-3,5,11-triene-1,1,8,8-tetracarboxylate
• 英文别名: tetramethyl (3E,5E,11Z)-11-methylcyclotetradeca-3,5,11-triene-1,1,8,8-tetracarboxylate
• CAS: 118089-46-6
• 化学式: C₂₃H₃₂O₈
• 分子量: 436.502
• InChiKey: RDNUWAQOLRKBFQ-WCPZEKIOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.06
• 重原子数：
  31.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  105.2
• 氢给体数：
  0.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  (3E,5E,11Z)-tetramethyl 11-methylcyclotetradeca-3,5,11-triene-1,1,8,8-tetracarboxylate 以53%的产率得到
  参考文献：
  名称：

  LAMOTHE, SERGE;NDIBWAMI, ALEXIS;DESLONGCHAMPS, PIERRE, TETRAHEDRON LETT., 29,(1988) N 14, 1641-1644

  摘要：

  DOI：
• 作为产物：
  描述：

  (Z)-tetramethyl 7-methyltetradeca-7-en-1,13-diyne-4,4,11,11-tetracarboxylate 在 bis-triphenylphosphine-palladium(II) chloride 、 一氯丙酮 、 potassium carbonate 作用下， 以 甲醇 、 水 为溶剂， 反应 12.08h， 以62%的产率得到(3E,5E,11Z)-tetramethyl 11-methylcyclotetradeca-3,5,11-triene-1,1,8,8-tetracarboxylate
  参考文献：
  名称：

  通过钯（II）催化的大环化提高环过Diels-Alder策略的效率

  摘要：

  钯（II）催化的双（乙烯基硼酸酯）化合物的大环化反应为跨环Diels-Alder反应底物提供了战略上有效的方法。在报道的几种系统中，大环是预先组织的，使得室温下的环加成与环化同时发生。与钯（0）催化的交叉偶联方法相比，具有许多优点。

  DOI：

  10.1021/ol303394t

文献信息

• Theoretical and Experimental Determination of the Effects Governing the Transannular Diels−Alder Reaction of Trans−Trans−Cis Systems with or without Activation of the Dienophile
  作者：Samuel Fortin、Louis Barriault、Yves L. Dory、Pierre Deslongchamps

  DOI：10.1021/ja0109491

  日期：2001.8.1

  A thorough study of the transannular Diels-Alder (TADA) reaction of trans-trans-cis macrocyclic trienes was carried out. It led to a better understanding of various parameters that govern the TADA reaction in particular and the Diels-Alder reaction in general. Thus, carbonyl activation of the dienophile and substitution of the diene are discussed, as well as the presence of substituents on the macrocycle

  对反-反-顺大环三烯的跨环狄尔斯-阿尔德（TADA）反应进行了深入研究。它有助于更​​好地了解控制 TADA 反应的各种参数，以及一般的 Diels-Alder 反应。因此，讨论了亲二烯体的羰基活化和二烯的取代，以及大环上取代基的存在及其在过渡态水平上的各自影响。
• Ndibwami, Alexis; Lamothe, Serge; Soucy, Pierre, Canadian Journal of Chemistry, 1993, vol. 71, # 5, p. 714 - 725
  作者：Ndibwami, Alexis、Lamothe, Serge、Soucy, Pierre、Goldstein, Solo、Deslongchamps, Pierre

  DOI：——

  日期：——
• Experimental and Semiempirical Calculation Studies of Transannular Diels-Alder and Other Competing Pericyclic Reactions
  作者：Yves L. Dory、Pierre Soucy、Marc Drouin、Pierre Deslongchamps

  DOI：10.1021/ja00106a060

  日期：1995.1

  Several related macrocyclic trienes have been found to interconvert thermally via [1,5]sigmatropic hydrogen shifts at the diene sites. These macrocyclic trienes further undergo thermal transannular Diels-Alder cycloaddition, thus yielding complex mixtures of adducts. This difficult problem has been tackled and qualitatively solved by means of the semiempirical methods AM1 and PM3. Most of the starting material ground states have been characterized as well as all the [1,5]sigmatropic hydrogen shift and Diels-Alder transition structures. The results of these calculations indicate that some [1,5]sigmatropic hydrogen shift enthalpies of activation are within the same range of most Diels-Alder enthalpies of activation. As a result the Curtin-Hammett principle does not apply for the entire system but only on limited regions. The method proved successful in uncovering the previously missassigned identity of one of the Diels-alder adducts: an unexpected 5-6-7-membered tricycle.