methyl (2E,4E)-hexa-2,4-dien-1-yl fumarate | 321350-76-9

• 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: methyl (2E,4E)-hexa-2,4-dien-1-yl fumarate
• 英文别名: 4-O-[(2E,4E)-hexa-2,4-dienyl] 1-O-methyl (E)-but-2-enedioate
• CAS: 321350-76-9
• 化学式: C₁₁H₁₄O₄
• 分子量: 210.23
• InChiKey: FPUXFIXDSBVMQI-ARQDATDDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  15
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.27
• 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：

  methyl (2E,4E)-hexa-2,4-dien-1-yl fumarate 以 甲苯 为溶剂， 反应 23.0h， 生成 methyl (3aR,4R,5R,7aS)-5-methyl-3-oxo-3a,4,5,7a-tetrahydro-1H-2-benzofuran-4-carboxylate 、
  参考文献：
  名称：

  对 1,3,8-壬三烯的分子内 Diels-Alder 反应的内-外立体选择性的新见解

  摘要：

  B3LYP/6-31G(d) 理论预测了 C9 取代的 1,3,8-壬三烯的分子内 Diels-Alder 反应的实验内-外选择性：反应是一致的，但过渡结构是显着异步的。

  DOI：

  10.1039/b006483l
• 作为产物：
  描述：

  (2E,4E)-2,4-己二烯-1-醇 、 富马酸单甲酯 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 3.5h， 以88%的产率得到methyl (2E,4E)-hexa-2,4-dien-1-yl fumarate
  参考文献：
  名称：

  Microwave-assisted tandem Wittig–intramolecular Diels–Alder cycloaddition. Product distribution and stereochemical assignment

  摘要：

  The IMDA cycloadditions of 10 different ester-tethered 1,3,8-nonatrienes have been examined under controlled microwave heating (MeCN, 180 degrees C, 30 min), giving 90-99% yields, and the stereochemical outcome of the exo and endo adducts established together with X-ray crystal structural analysis. A microwave-assisted tandem Wittig-IMDA cycloaddition protocol has been established for a modular synthesis of the bicyclic lactones starting from alpha-bromoacetates of 2,4-pentadien-1-ols and alpha-oxo carbonyl compounds in the presence of PPh3 and 2,6-lutidine (MeCN, 180 degrees C, 30 min). The overall yields of the tandem reactions are 68-80% and the stereoselectivity of the major adducts formed from E-substituted 1,3,8-nonatriene is the same as that observed for the purified 1,3,8-nonatrienes. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.06.039

文献信息

• A Combined Computational–Experimental Study of the Kinetics of Intramolecular Diels–Alder Reactions in a Series of 1,3,8-Nonatrienes
  作者：William J. Lording、Alan D. Payne、Tory N. Cayzer、Michael S. Sherburn、Michael N. Paddon-Row

  DOI：10.1071/ch14430

  日期：——

  Activation enthalpies for a series of five 1,3,8-nonatriene intramolecular Diels–Alder (IMDA) reactions involving substrates 1–5 have been determined experimentally and Singleton’s natural abundance method has been employed to determine kinetic isotope effects in the IMDA reaction of fumarate 3. The activation enthalpies for the IMDA reactions of the systems possessing a –CH2OCH2– diene/dienophile tether are

  活化焓为一系列涉及基板5 -1,3,8- nonatriene分子内狄尔斯-阿尔德（IMDA）反应1 - 5已被实验确定的和单件的天然丰度的方法已被用来确定在富马酸的IMDA反应动力学同位素效应3。具有–CH 2 OCH 2 –二烯/二烯系链的体系的IMDA反应的活化焓明显小于具有–CH 2的体系OC（= O）–系链。实验性的活化焓已被用于对四种模型化学的计算值进行基准测试，即两种密度泛函理论泛函B3LYP和M06-2X，以及两种通常非常准确的复合从头算函数函数CBS-QB3和G4（MP2）。G4（MP2）的性能优于计算上更昂贵的CBS-QB3方法，但是便宜得多的M06-2X / 6-31G（d）// B3LYP / 6-31G（d）方法足够准确，可以作为推荐的方法使用计算激活参数。富马酸酯3的IMDA反应的实验2 H动力学同位素效应证实了该Diels-Alder反应是一致但异步的计算预测。
• Intramolecular Diels−Alder Reactions of Ester-Linked 1,3,8-Nonatrienes
  作者：Tory N. Cayzer、Michael N. Paddon-Row、Damian Moran、Alan D. Payne、Michael S. Sherburn、Peter Turner

  DOI：10.1021/jo0505829

  日期：2005.7.1

  Penta-1,3-dienyl acrylates undergo kinetically controlled intramolecular Diels-Alder (lMDA) reactions and DFT calculations (B3LYP/6-31+G(d)) predict stereoselectivities that are in very good agreement with the experimental values. The nature of the diene Cl substituent has virtually no influence upon reactivity or trans/cis-stereoselectivity whereas terminal C9 dienophile substituents have a substantial effect on both the reactivity and stereoselectivity of these IMDA reactions. The TSs highlight contributions from strain in the developing tether-containing ring, and steric and electronic effects between tether and dienophile substituents, thus providing insight into the origins of IMDA reactivity and stereoselectivity.