dimethyl (E)-2-(3-phenylpropylidene)succinate

• 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: dimethyl (E)-2-(3-phenylpropylidene)succinate
• 英文别名: dimethyl (2E)-(3-phenylpropylidene)succinate；dimethyl-2-(3-phenylpropylidene)succinate；dimethyl (2E)-2-(3-phenylpropylidene)butanedioate
• 化学式: C₁₅H₁₈O₄
• 分子量: 262.306
• InChiKey: FUWIPTHEIFHORE-JLHYYAGUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  19
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  苯丙醛 、 1,4-dimethyl but-2-enedioate 在 三甲氧基硅烷 、 3-甲基-1-苯基-2-磷杂环戊烯-1-氧化物 、 苯甲酸 作用下， 以 甲苯 为溶剂， 反应 14.0h， 生成 dimethyl (Z)-2-(3-phenylpropylidene)succinate 、 dimethyl (E)-2-(3-phenylpropylidene)succinate
  参考文献：
  名称：

  新型无碱催化Wittig反应，用于合成高度官能化的烯烃

  摘要：

  已开发并优化了一种用于无碱催化Wittig反应的高效催化剂体系。最初，筛选了几种潜在的（预）催化剂以及不同的硅​​烷作为还原剂。基于容易获得的氧化膦作为前催化剂和三甲氧基硅烷作为还原剂的体系被证明是最佳的。研究了各种布朗斯台德酸性添加剂的效果。随后，优化反应条件并确定标准反应条件。在这些条件下，对该新协议的范围进行了评估。将九种活化烯烃和33种醛转化为42种高度官能化的烯烃。值得注意的是，可以将芳族，脂族和杂芳族醛进行转化，从而以高达99％的分离产率得到所需产物，并具有良好至优异的分离度。E / Z选择性。考虑到反应混合物的复杂性以及在一个罐中并行进行的四个反应步骤，这些结果强调了该方案的显着效率。

  DOI：

  10.1002/chem.201503744

文献信息

• Potassium Fluoride/Basic Alumina as Far Superior Heterogeneous Catalyst for the Chemoselective Conjugate Addition of Nitroalkanes to Electron-Poor Alkenes Having Two Electron-Withdrawing Groups in α- and β-Positions
  作者：Roberto Ballini、Alessandro Palmieri

  DOI：10.1002/adsc.200606105

  日期：2006.7

  The chemoselective, conjugate addition of nitroalkanes to electron-poor alkenes, with two electron-withdrawing groups in the α- and β-positions, can be easily performed at room temperature under solventless conditions using potassium fluoride/basic alumina as heterogeneous catalyst.

  使用氟化钾/碱性氧化铝作为多相催化剂，可在室温下于无溶剂条件下轻松地将硝基烷烃进行化学选择，共轭加成，并在α和β位置带有两个吸电子基团。
• First Base-Free Catalytic Wittig Reaction
  作者：Marie-Luis Schirmer、Sven Adomeit、Thomas Werner

  DOI：10.1021/acs.orglett.5b01352

  日期：2015.6.19

  The first base-free catalytic Wittig reaction utilizing readily available Bu3P (5 mol %) as an organocatalyst is reported. The initial Michael addition of the phosphine to a suitable acceptor substituted alkene ultimately results in the formation of an ylide which is subsequently converted with an aldehyde. The presented 1H NMR studies actually reveal evidence for the Michael addition and proposed

  报道了利用容易获得的Bu 3 P（5mol％）作为有机催化剂的第一无碱催化Wittig反应。将膦最初加成到合适的受体取代的烯烃上的迈克尔最终加成最终形成叶立德，其随后被醛转化。提出的1 H NMR研究实际上揭示了迈克尔加成反应和拟形成的内鎓盐的证据。在优化的反应条件下，将各种马来酸酯和富马酸酯用芳族，杂芳族和脂族醛进行转化，以评估这种前所未有的反应的范围和局限性。值得注意的是，马来酸盐和富马酸盐以立体会聚的方式反应。以高达95％的分离产率和E获得了相应的产物/ Z选择性高达99：1。
• Simultaneous presence of unsaturation and long alkyl chain at <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" altimg="si10.gif" overflow="scroll"><mml:mrow><mml:msubsup><mml:mrow><mml:mtext>P</mml:mtext></mml:mrow><mml:mrow><mml:mn>1</mml:mn></mml:mrow><mml:mrow><mml:mo>′</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math> of Ilomastat confers selectivity for gelatinase A (MMP-2) over gelatinase B (MMP-9) inhibition as shown by molecular modelling studies
  作者：Gautier Moroy、Clément Denhez、Haquima El Mourabit、Alix Toribio、Alexandra Dassonville、Martine Decarme、Jean-Hugues Renault、Catherine Mirand、Georges Bellon、Janos Sapi、Alain J.P. Alix、William Hornebeck、Erika Bourguet

  DOI：10.1016/j.bmc.2007.05.001

  日期：2007.7

  Structural analogues of Ilomastat (Galardin (R)), containing unsaturation(s) and chain extension carrying bulky phenyl group or alkyl moieties at P-1(') were synthesized and purified by centrifugal partition chromatography. They were analyzed for their inhibitory capacity towards MMP-1, MMP-2, MMP-3, MMP-9 and MMP-14, main endopeptidases involved in tumour progression. Presence of unsaturation(s) decreased the inhibitory potency of compounds but, in turn increased their selectivity for gelatinases. 2b and 2d derivatives with a phenyl group inhibited preferentially MMP-9 with IC50 equal to 45 and 38 nM, respectively, but also display activity against MMP-2 IC50 equal to 280 and 120 nM, respectively). Molecular docking computations confirmed affinity of these substances for both gelatinases. With aims to obtain a specific gelatinase A (MMP-2) inhibitor, P, of Ilomastat was modified to carry one unsaturation coupled to an alkyl chain with pentylidene group. Docking studies indicated that MMP-2, but not MMP-9, could accommodate such substitution; indeed 2a proved to inhibit MMP-2 (IC50 = 123 nM), while displaying no inhibitory capacity towards MMP-9. (c) 2007 Elsevier Ltd. All rights reserved.
• Novel Base-Free Catalytic Wittig Reaction for the Synthesis of Highly Functionalized Alkenes
  作者：Marie-Luis Schirmer、Sven Adomeit、Anke Spannenberg、Thomas Werner

  DOI：10.1002/chem.201503744

  日期：2016.2.12

  base‐free catalytic Wittig reactions has been developed and optimized. Initially, several potential (pre)catalysts as well as different silanes as reducing agents were screened. A system based on a readily available phosphine oxide as precatalyst and trimethoxy silane as reducing agent proved to be optimal. The effect of various Brønsted acidic additives was studied. Subsequently, the reaction conditions were

  已开发并优化了一种用于无碱催化Wittig反应的高效催化剂体系。最初，筛选了几种潜在的（预）催化剂以及不同的硅​​烷作为还原剂。基于容易获得的氧化膦作为前催化剂和三甲氧基硅烷作为还原剂的体系被证明是最佳的。研究了各种布朗斯台德酸性添加剂的效果。随后，优化反应条件并确定标准反应条件。在这些条件下，对该新协议的范围进行了评估。将九种活化烯烃和33种醛转化为42种高度官能化的烯烃。值得注意的是，可以将芳族，脂族和杂芳族醛进行转化，从而以高达99％的分离产率得到所需产物，并具有良好至优异的分离度。E / Z选择性。考虑到反应混合物的复杂性以及在一个罐中并行进行的四个反应步骤，这些结果强调了该方案的显着效率。