ethyl 2-(4-chlorophenyl)cyclopropanecarboxylate | 395683-40-6

• 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: ethyl 2-(4-chlorophenyl)cyclopropanecarboxylate
• 英文别名: ethyl (1S,2R)-2-(4-chlorophenyl)cyclopropane-1-carboxylate
• CAS: 395683-40-6
• 化学式: C₁₂H₁₃ClO₂
• 分子量: 224.687
• InChiKey: MBJPATUIODMIKJ-QWRGUYRKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  重氮乙酸乙酯 、 4-氯苯乙烯 在 thallium(I) hexafluorophosphate 、 RuCl[(S)-N,N'-(bis(o-(Ph₂P)PhCH)-6,6'-diMe-1,1'-biPh₂-diNH₂] 作用下， 以 二氯甲烷 为溶剂， 反应 14.0h， 生成 ethyl trans-2-(4-chlorophenyl)cyclopropane-1-carboxylate 、 ethyl cis-2-(4-chlorophenyl)cyclopropane-1-carboxylate 、 ethyl 2-(4-chlorophenyl)cyclopropanecarboxylate
  参考文献：
  名称：

  Strong Electronic Effects in thecis-Selective Asymmetric Cyclopropanation of Olefins Catalyzed by [RuCl(PNNP)]+

  摘要：

  The cationic [RuCl(PNNP)](+) catalysts containing tetradentate ligands with a P2N2 donor set (PNNP) show strong electronic effects in the cyclopropanation of para-substituted styrenes. The reactivity trend confirms that the carbene transfer to the olefin has electrophilic character. Linear free-energy relationships are observed for the relative reactivity, the cis/trans selectivity, and for the enantioselectivity (of the cis-cyclopropane). The linear correlation between log (k(X)/k(H)) and sigma shows a large value of rho (-2.4), which is indicative of significant charge buildup in the transition state of the carbene transfer to the olefin. All the relevant parameters (reactivity, diastereoselectivity, and enantioselectivity) increase with the increasing electron density at the C=C bond. To define the scope of the [RuCl(PNNP)](+) catalysts, 1- and 2-substituted styrenes, and oct-1-ene were also investigated.

  DOI：

  10.1002/1522-2675(20011017)84:10<3063::aid-hlca3063>3.0.co;2-r

文献信息

• Semi‐Rationally Designed Short Peptides Self‐Assemble and Bind Hemin to Promote Cyclopropanation
  作者：Oleksii Zozulia、Ivan V. Korendovych

  DOI：10.1002/anie.201916712

  日期：2020.5.18

  amyloid assemblies can impart a substantial degree of enantioselectivity without the need for extensive optimization; 3. The ease of peptide preparation allows for straightforward incorporation of unnatural amino acids and preparation of peptides made of D-amino acids with complete reversal of enantioselectivity.

  短肽的自组装产生了能够促进有效催化的通用纳米组装。我们半理性地设计了一系列七个残基的肽，这些肽可形成与血红素结合的催化淀粉样蛋白，以促进对映选择性环丙烷化，其效率可与工程化的血红素蛋白相媲美。这些结果表明：1.催化淀粉样蛋白可以结合复杂的金属因子以促进实际上重要的多底物转化。2.即使淀粉样蛋白组件的基本平坦的表面也可以赋予相当大的对映选择性，而无需进行广泛的优化。3.肽制备的容易性使得非天然氨基酸的直接掺入和由D-氨基酸制成的肽的制备具有对映选择性的完全逆转。
• Asymmetric Inter- and Intramolecular Cyclopropanation Reactions Catalyzed by a Reusable Macroporous-Polymer-Supported Chiral Ruthenium(II)/Phenyloxazoline Complex
  作者：Abdel-Moneim Abu-Elfotoh、Kesiny Phomkeona、Kazutaka Shibatomi、Seiji Iwasa

  DOI：10.1002/anie.201002240

  日期：2010.11.2

  Along came poly: A novel macroporous polymer‐supported chiral RuII/pheox catalyst (1, see SEM image) afforded excellent reactivity and enantioselectivity in inter‐ and intramolecular cyclopropanation reactions with a broad range of substrates. The catalyst showed no leaching and could be reused up to 11 times, even after storage.

  随之而来的是聚：一种新型的大孔聚合物负载的手性Ru II / pheox催化剂（1，参见SEM图片）在与多种底物的分子间和分子内环丙烷化反应中具有出色的反应性和对映选择性。该催化剂没有浸出，即使在储存后也可以重复使用多达11次。
• Chiral bipyridine–copper(II) complex. Crystal structure and catalytic activity in asymmetric cyclopropanation
  作者：Hoi-Lun Kwong、Wing-Sze Lee、Hung-Foon Ng、Wing-Hong Chiu、Wing-Tak Wong

  DOI：10.1039/a706754b

  日期：——

  A chiral bipyridine–copper(II) complex has been prepared and its crystal structure determined. The structure involves a CuN2Cl2 compressed tetrahedral stereochemistry. Chiral bipyridine complexes of copper-(I) and -(II) triflate are active catalysts for asymmetric cyclopropanation of alkenes with enantiomeric excesses up to 92%.

  制备了一种手性联吡啶-铜(II)配合物，并测定了其晶体结构。该结构涉及CuN2Cl2压缩四面体立体化学。三氟甲磺酸铜(I)和(II)的手性联吡啶配合物是对烯烃不对称环丙烷化反应的高活性催化剂，对映体过量率可达92%。
• Asymmetric cyclopropanation of olefins catalysed by Cu(<scp>i</scp>) complexes of chiral pyridine-containing macrocyclic ligands (Pc-L*)
  作者：Brunilde Castano、Stefano Guidone、Emma Gallo、Fabio Ragaini、Nicola Casati、Piero Macchi、Massimo Sisti、Alessandro Caselli

  DOI：10.1039/c2dt32347h

  日期：——

  The synthesis and characterisation of copper(I) complexes of chiral pyridine-containing macrocyclic ligands (Pc-L*) and their use as catalysts in asymmetric cyclopropanation reactions are reported. All ligands and metal complexes were fully characterised, including crystal structures of some species determined by X-ray diffraction on single crystals. This allowed characterising the very different conformations

  报道了手性含吡啶大环配体（Pc-L *）的铜（I）配合物的合成，表征及其在不对称环丙烷化反应中作为催化剂的应用。所有配体和金属络合物均得到充分表征，包括某些晶体的结构，这些晶体通过X射线衍射在单晶上确定。这允许表征大环的非常不同的构象，其可以由不同的取代基或金属络合诱导。配体合成所采用的策略非常灵活，可以进行多种结构修饰。具有相同供体性质但具有C 1或C 2的大环配体的小型文库 对称被合成。 环丙烷 具有良好收率的同时具有芳族和脂族烯烃的产物，对映体过量高达99％。
• Continuous flow asymmetric cyclopropanation reactions using Cu(<scp>i</scp>) complexes of Pc-L* ligands supported on silica as catalysts with carbon dioxide as a carrier
  作者：Brunilde Castano、Emma Gallo、David J. Cole-Hamilton、Vladimiro Dal Santo、Rinaldo Psaro、Alessandro Caselli

  DOI：10.1039/c4gc00119b

  日期：——

  Continuous flow heterogeneous asymmetric cyclopropanations catalysed by supported hydrogen-bonded (SHB) chiral copper(I) complexes of pyridine containing tetraazamacrocyclic ligands Pc-L* using CO2 as a transport vector are described. The catalytic system showed high stability and good recyclability without loss of activity for at least 24 h in CO2 and catalyst turnover numbers up to 440 were obtained

  描述了由含四氮杂大环配体Pc-L *的吡啶的负载氢键合（SHB）手性铜（I）配合物催化的连续流动非均相不对称环丙烷化反应，其中CO 2作为转运载体。该催化体系显示出高稳定性和良好的可回收性，在CO 2中至少保持24 h的活性不变，并且获得了高达440的催化剂周转率，且转化率（高达99％）和选择性（高达88％）高。没有观察到铜的浸出。来自芳族和脂族烯烃的环丙烷产物以良好的产率获得，对映体过量高达72％。