1r-benzoyl-2c,3t-diphenylcyclopropane | 26597-09-1

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 1r-benzoyl-2c,3t-diphenylcyclopropane
• 英文别名: (2,3-diphenylcyclopropyl)(phenyl)methanone；[(2R,3R)-2,3-diphenylcyclopropyl]-phenylmethanone
• CAS: 26597-09-1
• 化学式: C₂₂H₁₈O
• 分子量: 298.384
• InChiKey: VTKDKHYPPRDKPN-WOJBJXKFSA-N

物化性质

• 熔点：
  153 °C(Solv: ethanol (64-17-5))
• 沸点：
  441.5±45.0 °C(Predicted)
• 密度：
  1.153±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1r-benzoyl-2c,3t-diphenylcyclopropane 以 正己烷 、 二氯甲烷 为溶剂， 生成 cis-2,3-diphenyl-1-benzoylcyclopropane
  参考文献：
  名称：

  Enhanced Diastereoselectivity via Confinement:  Diastereoselective Photoisomerization of 2,3-Diphenyl-1-benzoylcyclopropane Derivatives within Zeolites

  摘要：

  Photochemistry of optically pure trans-2,3-diphenyl-1-benzoylcyclopropane has been examined in isotropic solution and within zeolites. Results suggest that it isomerizes by cleavage of either the C-1-C-2 or C-1-C-3 bond. From the perspective of chiral induction, photoisomerization of cis-2,3-diphenyl-1-benzoylcyclopropane derivatives with chiral auxiliaries placed at the meta and para positions of the benzoyl group have been examined both in isotropic solution and within zeolites. Whereas in isotropic solution the chiral auxiliaries placed at the meta position exhibit very little influence during the conversion of triplet cis-2,3-diphenyl-1-benzoylcyclopropane derivatives, they have significant influence within zeolites. For example, a-methyl benzylamine placed at the meta position of the benzoyl group (via an amide bond) yields the trans isomer with a diastereoselectivity (de) of 71% within NaY zeolite, whereas in solution no de is obtained. The chiral induction process within zeolites depends on the nature of the alkali ion and on the presence of water. Results suggest that the chiral auxiliary is able to control the bond being cleaved (C-1-C-2 VS. C-1-C-3 bond) within a zeolite, but it is unable to do so in an isotropic solution.

  DOI：

  10.1021/jo049697n
• 作为产物：
  描述：

  苯甲醛腙 在 sodium hydroxide 、 mercury(II) oxide 作用下， 以 乙醚 、 二丁醚 为溶剂， 反应 16.83h， 生成 1r-benzoyl-2c,3t-diphenylcyclopropane
  参考文献：
  名称：

  Phosphoranylidenehydrazones as in situ sources of diazo compounds: a facile synthesis of aryl-substituted benzoylcyclopropanes

  摘要：

  DOI：

  10.1021/jo00162a033

文献信息

• Radical Cation Cyclopropanations via Chromium Photooxidative Catalysis
  作者：Francisco J. Sarabia、Eric M. Ferreira

  DOI：10.1021/acs.orglett.7b01095

  日期：2017.6.2

  The chromium photocatalyzed cyclopropanation of diazo reagents with electron-rich alkenes is described. The transformation occurs under mild conditions and features specific distinctions from traditional diazo-based cyclopropanations (e.g., avoiding β-hydride elimination, chemoselectivity considerations, etc.). The reaction appears to work most effectively using chromium catalysis, and a number of

  描述了重氮试剂与富电子烯烃的铬光催化环丙烷化反应。该转化发生在温和的条件下，并具有与传统重氮基环丙烷化的特定区别（例如，避免β-氢化物消除、化学选择性考虑等）。该反应似乎在铬催化下最有效地进行，并且可以以通常良好的产率获得许多修饰的环丙烷。
• Catalytic cyclopropanation of electron deficient alkenes mediated by chiral and achiral sulfides: scope and limitations in reactions involving phenyldiazomethane and ethyl diazoacetate
  作者：Varinder K. Aggarwal、Helen W. Smith、George Hynd、Ray V. H. Jones、Robin Fieldhouse、Sharon E. Spey

  DOI：10.1039/b004367m

  日期：——

  Phenyldiazomethane reacts with electron deficient alkenes in the presence of catalytic amounts of transition metal catalyst [Rh2(OAc)4 was better than Cu(acac)2] and catalytic amounts of sulfide to give cyclopropanes. Pentamethylene sulfide was found to be superior to tetrahydrothiophene and the optimum solvent was toluene. Under these optimised conditions a range of enones were cyclopropanated in

  苯重氮甲烷 与电子缺乏反应 烯烃 在催化量的过渡金属存在下 催化剂[Rh 2（OAc）4优于Cu（acac）2 ]和硫化物的催化量得到环丙烷。 五甲基亚砜 被发现优于 四氢噻吩 和最佳 溶剂 曾是 甲苯。在这些优化条件下，烯酮进行了高产率的环丙烷化。循环的烯酮丙烯酸酯在此过程中不成功。衍生自手性的1,3-氧杂蒽的用途樟脑磺酰氯 在此过程中分两步进行 环丙烷具有良好的收率和很高的对映体过量（> 97％ee）。的绝对立体化学环丙烷 10被证明X射线分析立体化学诱导的来源已经合理化。这项工作扩展到包括重氮酯，是部分成功的。再次五亚甲基硫醚 被发现优于 四氢噻吩，但这次发现Rh 2（OAc）4和Cu（acac）2都同样有效。烯酮，富马酸和不饱和 硝基化合物 效果很好，但简单的丙烯酸酯和不饱和丙烯酸酯 醛类不是有效的底物。进行了对照实验，其中稳定的叶立德 分离并与不太成功的底物反应，而不饱和 醛类
• Organoselenium-Catalyzed Asymmetric Cyclopropanations of (<i>E</i>)-Chalcones
  作者：Pei-Tung Cheng、Yu-Hsun Tseng、Rong-Jie Chein

  DOI：10.1021/acs.orglett.1c03243

  日期：2021.10.15

  compounds were used to catalyze asymmetric cyclopropanation reactions; the selenonium ylide intermediates formed from these selenium-containing catalysts and benzyl bromide efficiently react with (E)-chalcones to give various cyclopropanes (27 examples) with excellent enantioselectivities of ≤99% ee and are the first examples of organoselenium-catalyzed asymmetric cyclopropanations.

  我们报告了一类新的基于 ( S )-二苯基(四氢硒酚-2-基) 甲醇的手性四氢硒酚，其由 ( R )-3-(3-溴丙基)-2,2-二苯基环氧乙烷和硒化钠制备。这些手性四氢硒酚类化合物用于催化不对称环丙烷化反应；由这些含硒催化剂和苄基溴形成的硒叶立德中间体与 ( E )-查耳酮有效反应，得到各种环丙烷（27 个实例），具有≤99% ee 的优异对映选择性，是有机硒催化不对称环丙烷化的第一个实例。
• Cyclopropanation Reactions of Enones with Lithiated Sulfoximines:  Application to the Asymmetric Synthesis of Chiral Cyclopropanes
  作者：Stephen G. Pyne、Zemin Dong、Brian W. Skelton、Allan H. White

  DOI：10.1021/jo962216i

  日期：1997.4.1

  kinetically controlled conditions. At rt the initially formed anionic Michael adducts undergo intramolecular displacement of the sulfonimidoyl group, with inversion of stereochemistry at the carbon bearing the nucleofuge, to give cyclopropanes. Lithiated sulfoximines derived from S-alkyl sulfoximines give mixtures of 1,2- and 1,4-adducts with enones under kinetically controlled conditions. However, at rt

  在动力学控制的条件下，稳定的锂化亚砜亚砜2和9与非环烯酮进行高度非对映选择性Michael反应。在室温下，最初形成的阴离子迈克尔加合物经历了磺酰亚胺基的分子内置换，同时带有核试剂的碳上的立体化学转化，从而生成环丙烷。在动力学控制的条件下，衍生自S-烷基亚磺酰亚胺的锂化亚磺酰亚胺产生1,2-和1,4-加合物与烯酮的混合物。但是，在室温下，1,2-加合物与其相应的1,4-加合物处于平衡状态。1,4-加合物以高度非对映选择性的方式形成，并以良好或优异的收率迅速转化为非对映体纯的环丙烷。这些亚砜亚胺的旋光形式可得到高对映体纯度的环丙烷。
• Study on the Reactions of Telluronium Ylide VIII. A Facile Synthesis of Substituted Cyclopropanes
  作者：Qi Zhong、Jianguo Shao、Changqing Liu

  DOI：10.1080/00397919208019247

  日期：1992.2

  Abstract Some telluronium salts react easily with substituted chalcones to afford derivatives of cyclopropane in 52–95% yield and with high stereoselectivity.

  摘要 一些碲盐很容易与取代的查耳酮反应，以 52-95% 的收率和高立体选择性得到环丙烷衍生物。