2-(1-methyl-3-phenylallyl)malonic acid dimethyl ester | 87802-86-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-(1-methyl-3-phenylallyl)malonic acid dimethyl ester
• 英文别名: dimethyl 2-(4-phenylbut-3-en-2-yl)malonate；dimethyl (4-phenyl-3-buten-2-yl)malonate；Dimethyl 2-(4-phenylbut-3-en-2-yl)propanedioate
• CAS: 87802-86-6
• 化学式: C₁₅H₁₈O₄
• 分子量: 262.306
• InChiKey: FQUOZEVDJXQKDV-UHFFFAOYSA-N

物化性质

• 沸点：
  210 °C(Press: 34 Torr)
• 密度：
  1.105±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  19
• 可旋转键数：
  7
• 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：

  (phenyl-methyl-π-allyl)dicarbonylnitrosyl iron 、 丙二酸二甲酯 在 lithium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 16.0h， 以62%的产率得到2-(1-methyl-3-phenylallyl)malonic acid dimethyl ester
  参考文献：
  名称：

  Reactivity of (η3-allyl)dicarbonylnitrosyl iron complexes with dimethyl malonate and diisobutyl malonate

  摘要：

  在本文中，我们描述了我们之前报道的（η3-烯丙基）二羰基亚硝基铁配合物（1–9）的反应性。在此背景下，进行了1–9与二甲基马来酸酯和二异丁基马来酸酯的化学计量反应。通过气相色谱分析反应混合物，确定了所得到的产物（10–25）的区域选择性。这些产物通过柱色谱纯化，然后通过红外光谱、1H NMR、13C NMR光谱和质谱进行结构表征。也研究了不同配体L（L = CO, PPh3, SIMES (1,3-二-tert-丁基咪唑氟磷酸盐), BUSI（1,3-双（2,4,6-三甲基苯）-4,5-二氢-3H-咪唑-1-氟磷酸盐））及其对取代模式的影响。引入可变取代基表现出多样的反应性。一般观察到，通过增大取代基的大小，(η3-烯丙基)二羰基亚硝基铁配合物（1–9）的反应性降低。由于烯丙基部分的取代模式，对反应性产生了明显的影响。从C-3位置移位到C-2位置时，转化率从81%显著降低至68%。

  DOI：

  10.4314/bcse.v31i2.11

文献信息

• Asymmetric allylic substitutions on symmetrical and non-symmetrical substrates using [5]ferrocenophane ligands
  作者：Radovan Šebesta、Andrea Škvorcová、Branislav Horváth

  DOI：10.1016/j.tetasy.2010.05.054

  日期：2010.8

  A series of [5]ferrocenophane diphosphane ligands were used in Pd-catalyzed allylic substitution reactions. With a symmetrical substrate, 1,3-diphenylpropenyl acetate, enantioselectivities between 70% and 94% ee were observed. Several non-symmetrically substituted allylic substrates were also used. Depending on the substituents of the non-symmetrical allylic substrates, various degrees of regioselectivity (from 1:1 to 100:0) and enantioselectivity (from 0% to 96% ee) were observed. Tentative catalytically active complexes were studied by DFT computational methods. (C) 2010 Elsevier Ltd. All rights reserved.
• Influence of structural changes in ferrocene phosphane aminophosphane ligands on their catalytic activity
  作者：Radovan Šebesta、Andrea Škvorcová

  DOI：10.1016/j.jorganchem.2009.01.027

  日期：2009.5

  New phosphane aminophosphane ligands based on [3]ferrocenophane skeleton were synthesized using a direct double lithiation followed by phosphanylation. Influence of ligand structure on catalytic performance was evaluated by performing a series of Pd-catalyzed allylic substitution on different substrates. Enantioselectivities up to 55% ee were obtained with bridged ligand compared to 33% ee with analogous non-bridged BoPhoz ligand. (C) 2009 Elsevier B.V. All rights reserved.
• Reactivity of (η3-allyl)dicarbonylnitrosyl iron complexes with dimethyl malonate and diisobutyl malonate
  作者：M. Tabassam、A. Farooq、M. Imran、S. R. Gillani、S. Saqib、Z. Mehmood、L. Mitu

  DOI：10.4314/bcse.v31i2.11

  日期：——

  In this paper, we describe the reactivity of our previously reported (η3-allyl)dicarbonylnitrosyl iron complexes (1–9). In this context, stoichiometric reactions of 1–9 with dimethyl malonate and di-iso-butyl malonate were carried out. The regioselectivity of the resulting products (10–25) was determined by gas chromatoraphic analysis of reaction mixtures. These products were purified by column chromatography and then structurally characterized by IR, 1H NMR, 13C NMR spectroscopies and mass spectrometry. Effect of different ligands L (L = CO, PPh3, SIMES (1,3-di-tert-butylimidazolium hexafluoro phosphate), BUSI(1,3-bis(2,4,6-trimethyl-phenyl)-4,5-dihydro-3H-imidazol-1-ium hexafluorophosphate)) and their influence on the substitution pattern has also been studied. The introduction of variable substituents exhibited diverse reactivities. Generally, it was observed that the reactivity decreased by increasing the size of substituentin (η3-allyl)dicarbonylnitrosyl iron complexes (1–9). Strong impact on the reactivity was observed due to substitution pattern of the allyl moiety. A considerable reduction in the conversion ratio from 81% to 68% was observed in repositioning the substituent from C-3 to C-2 position.

  在本文中，我们描述了我们之前报道的（η3-烯丙基）二羰基亚硝基铁配合物（1–9）的反应性。在此背景下，进行了1–9与二甲基马来酸酯和二异丁基马来酸酯的化学计量反应。通过气相色谱分析反应混合物，确定了所得到的产物（10–25）的区域选择性。这些产物通过柱色谱纯化，然后通过红外光谱、1H NMR、13C NMR光谱和质谱进行结构表征。也研究了不同配体L（L = CO, PPh3, SIMES (1,3-二-tert-丁基咪唑氟磷酸盐), BUSI（1,3-双（2,4,6-三甲基苯）-4,5-二氢-3H-咪唑-1-氟磷酸盐））及其对取代模式的影响。引入可变取代基表现出多样的反应性。一般观察到，通过增大取代基的大小，(η3-烯丙基)二羰基亚硝基铁配合物（1–9）的反应性降低。由于烯丙基部分的取代模式，对反应性产生了明显的影响。从C-3位置移位到C-2位置时，转化率从81%显著降低至68%。