2-(3-methylbut-2-enyl)-2-oxiranylmethylmalonic acid diethyl ester | 499193-30-5

• 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: 2-(3-methylbut-2-enyl)-2-oxiranylmethylmalonic acid diethyl ester
• 英文别名: Diethyl 2-(3-methylbut-2-enyl)-2-(oxiran-2-ylmethyl)propanedioate
• CAS: 499193-30-5
• 化学式: C₁₅H₂₄O₅
• 分子量: 284.353
• InChiKey: LTHFDYVVIIKNJB-UHFFFAOYSA-N

物化性质

• 沸点：
  327.8±22.0 °C(Predicted)
• 密度：
  1.077±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  20
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  65.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-(3-methylbut-2-enyl)-2-oxiranylmethylmalonic acid diethyl ester 在 二氯二茂钛 、 锰 、 collidine hydrochloride 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以67%的产率得到diethyl-1,1-dimethyltetrahydro-1H-cyclopenta[c]furan-5,5(3H)-dicarboxylate
  参考文献：
  名称：

  一个前所未有的串联反应的激进回旋处，包括钛-氧键的均裂取代

  摘要：

  描述了具有苄基、仲烷基和叔烷基自由基的 ClCp2Ti-O 键的概念新颖的均裂取代 (SH2)。通过 DFT 方法研究了中间体和关键的过渡结构。由此产生的原子经济自由基串联反应可用于从简单的起始材料合成结构复杂的四氢呋喃，因此对天然产物合成很感兴趣。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

  DOI：

  10.1002/ejoc.200400001
• 作为产物：
  描述：

  ethyl (±)-4,5-epoxy-2-(ethoxycarbonyl)pentanoate 、 1-溴-3-甲基-2-丁烯 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以79%的产率得到2-(3-methylbut-2-enyl)-2-oxiranylmethylmalonic acid diethyl ester
  参考文献：
  名称：

  A comparison of electron transfer reagents in the reductive opening of epoxides: reasons for the superiority of titanocene based complexes

  摘要：

  Several commonly used electron transfer reagents were compared in their reactivity towards three epoxides. These substrates were designed to allow for a distinction between competing courses of the reaction. It was found that titanocene reagents were clearly superior due to their low Lewis acidity, high reduction tendency towards epoxides, and low reduction tendency towards the pivotal P-metal oxy radical intermediates. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(02)00697-x

文献信息

• A Radical Roundabout for an Unprecedented Tandem Reaction Including a Homolytic Substitution with a Titanium-Oxygen Bond
  作者：Andreas Gansäuer、Björn Rinker、Noëllie Ndene-Schiffer、Marianna Pierobon、Stefan Grimme、Mareike Gerenkamp、Christian Mück-Lichtenfeld

  DOI：10.1002/ejoc.200400001

  日期：2004.6

  Conceptually novel homolytic substitutions (SH2) of ClCp2Ti−O bonds with benzylic, secondary and tertiary alkyl radicals are described. The intermediates and crucial transition structures were studied by DFT methods. The resulting atom economical radical tandem reaction can be utilized for the synthesis of structurally complex tetrahydrofurans from simple starting materials and is therefore of interest

  描述了具有苄基、仲烷基和叔烷基自由基的 ClCp2Ti-O 键的概念新颖的均裂取代 (SH2)。通过 DFT 方法研究了中间体和关键的过渡结构。由此产生的原子经济自由基串联反应可用于从简单的起始材料合成结构复杂的四氢呋喃，因此对天然产物合成很感兴趣。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
• Catalysis via Homolytic Substitutions with C−O and Ti−O Bonds: Oxidative Additions and Reductive Eliminations in Single Electron Steps
  作者：Andreas Gansäuer、André Fleckhaus、Manuel Alejandre Lafont、Andreas Okkel、Konstantinos Kotsis、Anakuthil Anoop、Frank Neese

  DOI：10.1021/ja907817y

  日期：2009.11.25

  In a combined theoretical and experimental study, an efficient catalytic reaction featuring epoxide opening and tetrahydrofuran formation through homolytic substitution reactions at C-O and Ti-O bonds was devised. The performance of these two key steps of the catalytic cycle was studied and could be adjusted by modifying the electronic properties of the catalysts through introduction of electron-donating or -withdrawing substituents to the titanocene catalysts. By regarding both steps as single electron versions of oxidative addition and reductive elimination, a mechanism-based platform for the design of catalysts and reagents-for electron transfer reactions evolved that opens broad perspectives for further investigations.
• A Radical Tandem Reaction with Homolytic Cleavage of a TiO Bond
  作者：Andreas Gansäuer、Björn Rinker、Marianna Pierobon、Stefan Grimme、Mareike Gerenkamp、Christian Mück-Lichtenfeld

  DOI：10.1002/anie.200351240

  日期：2003.8.11
• Cp ₂ TiX Complexes for Sustainable Catalysis in Single‐Electron Steps
  作者：Ruben B. Richrath、Theresa Olyschläger、Sven Hildebrandt、Daniel G. Enny、Godfred D. Fianu、Robert A. Flowers、Andreas Gansäuer

  DOI：10.1002/chem.201705707

  日期：2018.4.25

  electrochemical, kinetic, and synthetic study with a novel and easily accessible class of titanocene catalysts for catalysis in single‐electron steps. The tailoring of the electronic properties of our Cp2TiX‐catalysts that are prepared in situ from readily available Cp2TiX2 is achieved by varying the anionic ligand X. Of the complexes investigated, Cp2TiOMs proved to be either equal or substantially superior to

  我们提出了一种结合电化学，动力学和合成的研究方法，并使用新颖且易于使用的一类钛茂催化剂在单电子步骤中进行催化。我们的Cp的电子性质的剪裁2被原位制备从容易获得的Cp TIX催化剂2 TIX 2通过改变阴离子配体X中的复合物的实现研究中，Cp 2事实证明，TiOMs等于或远远优于早期开发的最佳催化剂。已经确定了与催化有关的动力学和热力学性质。它们使机械理解有效的氧化添加和还原所需的特性之间的细微相互作用。因此，我们的研究突出了有效的催化剂不需要对环戊二烯基配体进行精细的共价修饰。
• A comparison of electron transfer reagents in the reductive opening of epoxides: reasons for the superiority of titanocene based complexes
  作者：Andreas Gansäuer、Björn Rinker

  DOI：10.1016/s0040-4020(02)00697-x

  日期：2002.8

  Several commonly used electron transfer reagents were compared in their reactivity towards three epoxides. These substrates were designed to allow for a distinction between competing courses of the reaction. It was found that titanocene reagents were clearly superior due to their low Lewis acidity, high reduction tendency towards epoxides, and low reduction tendency towards the pivotal P-metal oxy radical intermediates. (C) 2002 Elsevier Science Ltd. All rights reserved.