dimethyl 2-(phenylethynyl)cyclopropane-1,1-dicarboxylate | 1206604-33-2

• 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: dimethyl 2-(phenylethynyl)cyclopropane-1,1-dicarboxylate
• 英文别名: dimethyl 2-(2-phenylethynyl)cyclopropane-1,1-dicarboxylate；Dimethyl 2-(2-phenylethynyl)cyclopropane-1,1-dicarboxylate
• CAS: 1206604-33-2
• 化学式: C₁₅H₁₄O₄
• 分子量: 258.274
• InChiKey: KJNNHCJIOFHTHK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• 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

• 作为反应物：
  描述：

  dimethyl 2-(phenylethynyl)cyclopropane-1,1-dicarboxylate 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以96%的产率得到(2-(phenylethynyl)cyclopropane-1,1-diyl)dimethanol
  参考文献：
  名称：

  Tetrahydro-1,3-oxazepines via Intramolecular Amination of Cyclopropylmethyl Cation

  摘要：

  An efficient synthesis of tetrahydro-1,3-oxazepines was developed involving the regioselective intramolecular amination of cyclopropylmethyl cation. The cation was generated by the abstraction of one imidate group in bis-imidate bearing a carbocation-stabilizing substituent. Using 1,1,2,3-tetrasubstituted cyclopropane substrates, highly diastereoselective intramolecular amination to trans-tetrahydro-1,3-oxazepines was achieved. The resulting tetrahydro-1,3-oxazepines were transformed to the homoallylamine derivatives in high yields.

  DOI：

  10.1021/acs.orglett.5b01014
• 作为产物：
  描述：

  苯乙炔 在 dirhodium tetraacetate 、 copper(l) iodide 、 四(三苯基膦)钯 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 20.0h， 生成 dimethyl 2-(phenylethynyl)cyclopropane-1,1-dicarboxylate
  参考文献：
  名称：

  铑（III）催化的连续C–H / C–C活化与N-芳氧基酰胺对炔基环丙烷的氧化还原中性环化

  摘要：

  炔基环丙烷首次在过渡金属催化的C–H功能化中作为偶联伙伴使用。特别是，已开发出Cp * Rh III催化的N-芳氧基酰胺与炔基环丙烷的区域选择性环氧化反应，通过氧化还原中性的C–H / C–C活化作用，可提供高度官能化的带有（E）-外环碳的2,3-二氢苯并呋喃。–碳双键和四取代碳中心，具有中等到良好的产率，具有广泛的底物范围。

  DOI：

  10.1021/acs.joc.8b02661

文献信息

• Cascade Cleavage of Three-Membered Rings in the Reaction of D–A Cyclopropanes with 4,5-Diazaspiro[2.4]hept-4-enes: A Route to Highly Functionalized Pyrazolines
  作者：Roman A. Novikov、Denis D. Borisov、Maria A. Zotova、Dmitry A. Denisov、Yaroslav V. Tkachev、Victor A. Korolev、Evgeny V. Shulishov、Yury V. Tomilov

  DOI：10.1021/acs.joc.8b00725

  日期：2018.8.3

  A new cascade process for reactions of donor–acceptor cyclopropanes (DACs) with spiro[cyclopropanepyrazolines] in the presence of EtAlCl2 or Ga halides is reported. The action of a Lewis acid results in DAC activation and addition of the carbocationic intermediate to the azocyclopropane system of the pyrazoline with opening of the second three-membered ring and addition of a halide anion from the Lewis

  EtAlCl 2存在下供体-受体环丙烷（DAC）与螺[环丙烷吡唑啉]反应的新级联过程或报道卤化镓。路易斯酸的作用导致DAC活化，并将碳阳离子中间体加到吡唑啉的偶氮环丙烷系统中，同时打开第二个三元环，并从路易斯酸中加入卤化物阴离子。该方法的一个特定特征是一个活化的环丙烷环会活化另一个环丙烷，并且取决于组分比率，该方法可能涉及两个DAC分子和一个吡唑啉分子或一个DAC分子和两个吡唑啉分子。该方法可耐受各种官能团，并且可与多种底物发生，从而产生基于2-吡唑啉部分的多官能化结构。
• Ruthenium-Triggered Ring Opening of Ethynylcyclopropanes: [3+2] Cycloaddition with Aldehydes and Aldimines Involving Metal Allenylidene Intermediates
  作者：Yoshihiro Miyake、Satoshi Endo、Taichi Moriyama、Ken Sakata、Yoshiaki Nishibayashi

  DOI：10.1002/anie.201207801

  日期：2013.2.4

  It's complex: Ruthenium‐catalyzed [3+2] cycloaddition of ethynylcyclopropanes with aldehydes and aldimines has been found to give the corresponding 2‐ethynyltetrahydrofurans or ‐pyrrolidines in high to excellent yields. In both cases, the formation of a ruthenium allenylidene complex as a key reactive intermediate is supported by density functional theory calculations. Cp*=η5‐C5Me5.

  它很复杂：发现乙炔基环丙烷与钌和醛亚胺在钌催化的[3 + 2]环加成反应中，可以以高产率或优异产率得到相应的2-乙炔基四氢呋喃或吡咯烷。在这两种情况下，密度泛函理论计算都支持了钌烯基亚烷基络合物作为关键的反应性中间体的形成。的Cp * =η 5 -C 5我5。
• Asymmetric (5 + 3) Annulation of Donor–Acceptor Cyclopropanes with Imidazolidines: Access to Saturated 1,4-Diazocanes
  作者：Liangliang Yang、Jieyin He、Haiyang Wang、Wendi Xu、Xue Zhang、Ming Lang、Jian Wang、Shiyong Peng

  DOI：10.1021/acscatal.3c01219

  日期：2023.4.21

  Saturated 1,4-diazocanes are highly important for medicinal chemistry and drug discovery, but their syntheses are often tedious. Herein, we report a copper-catalyzed (5 + 3) annulation of donor–acceptor cyclopropanes with imidazolidines, thereby providing a straightforward method to access a library of saturated 1,4-diazocanes in moderate to excellent yields under mild reaction conditions. More importantly

  饱和 1,4-重氮烷对药物化学和药物发现非常重要，但它们的合成通常很乏味。在此，我们报告了铜催化的供体-受体环丙烷与咪唑啉的 (5 + 3) 环化反应，从而提供了一种在温和反应条件下以中等至优异的收率获取饱和 1,4-重氮烷库的直接方法。更重要的是，这种导致光学活性饱和 1,4-重氮烷的 (5 + 3) 环化的不对称版本是通过两种策略实现的：(i) 手性转移和 (ii) 通过使用三氟甲磺酸铜和 SaBOX 进行动态动力学不对称转换配体。此外，还实现了供体-受体环丙烷与六氢嘧啶的类似 (6 + 3) 环化。
• Synthesis of Enantioenriched Allenes from 1,1-Cyclopropanediesters
  作者：Pascal Cérat、Philipp J. Gritsch、Sébastien R. Goudreau、André B. Charette

  DOI：10.1021/ol902766f

  日期：2010.2.5

  Highly substituted allenes were obtained by the S(N)2' addition of organocuprate reagents on 2-propargyl-1,1-cyclopropanediesters. This new methodology permits the synthesis of highly enantioenriched allenes as the reaction proceeds with retention of the enantiomeric purity of the starting cyclopropane. The use of higher order cuprates was instrumental in obtaining the reported results.
• Tetrahydro-1,3-oxazepines via Intramolecular Amination of Cyclopropylmethyl Cation
  作者：Marija Skvorcova、Liene Grigorjeva、Aigars Jirgensons

  DOI：10.1021/acs.orglett.5b01014

  日期：2015.6.19

  An efficient synthesis of tetrahydro-1,3-oxazepines was developed involving the regioselective intramolecular amination of cyclopropylmethyl cation. The cation was generated by the abstraction of one imidate group in bis-imidate bearing a carbocation-stabilizing substituent. Using 1,1,2,3-tetrasubstituted cyclopropane substrates, highly diastereoselective intramolecular amination to trans-tetrahydro-1,3-oxazepines was achieved. The resulting tetrahydro-1,3-oxazepines were transformed to the homoallylamine derivatives in high yields.