cis-2,3-diphenyl-1-benzoylcyclopropane | 17608-67-2

• 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: cis-2,3-diphenyl-1-benzoylcyclopropane
• 英文别名: ((1r,2R,3S)–2,3–diphenylcyclopropyl)(phenyl)methanone；1r-benzoyl-2t,3t-diphenylcyclopropane；2,3-diphenyl-1-benzoylcyclopropane
• CAS: 17608-67-2
• 化学式: C₂₂H₁₈O
• 分子量: 298.384
• InChiKey: VTKDKHYPPRDKPN-AERCQKQUSA-N

物化性质

• 熔点：
  89 °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)：
  5.07
• 重原子数：
  23.0
• 可旋转键数：
  4.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  cis-2,3-diphenyl-1-benzoylcyclopropane 在 Rh(ttp)Me 、 异丙醇 作用下， 以 氘代苯 为溶剂， 反应 48.0h， 以40%的产率得到1,3,4-Triphenyl-butan-1-on
  参考文献：
  名称：

  铑卟啉用iPrOH催化环丙烷中C–Cσ键的区域选择性转移氢解

  摘要：

  发现了一种新的铑卟啉以i PrOH为氢源催化活化和未活化环丙烷的区域选择性转移氢解反应。通过用金属卟啉铑（II）进行初始自由基取代以生成卟啉烷基铑，然后用i PrOH氢解以生成相应的无环烷烃并再生铑，从而确定了环丙烷C–Cσ键活化的反应机理。（二）金属卟啉自由基。

  DOI：

  10.1021/acs.organomet.9b00290
• 作为产物：
  描述：

  trans-2,3-diphenylcyclopropane-1-carboxylic acid 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 1.0h， 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

文献信息

• 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。
• Reactions of Diazoketones in the Presence of Metal Chelates. II. Reactions with Olefinic Compounds
  作者：Matsuji Takebayashi、Toshikazu Ibata、Hideki Kohara、Kozaburo Ueda

  DOI：10.1246/bcsj.42.2938

  日期：1969.10

  The reaction of α-diazoacetophenone with olefinic compounds, such as vinyl acetate, cis- and trans-stilbenes and cyclohexene, has been studied in the presence of bis(acetylacetonato)copper-(II). The reaction gave the corresponding cyclopropane derivatives, the addition products of benzoylcarbene to the double bond of olefinic compounds in good yields, accompanied by cis-and trans-dibenzoylethylenes, dibenzoylethane or dilactone. Addition of carbene was found to be stereospecific in the cases of cis- and trans-stilbenes. A mechanism has been advanced in which a ketocarbene-metal chelate complex is included as an intermediate of the reaction.

  在双(乙酰丙酮)铜-(II)存在下，研究了α-重氮苯乙酮与烯属化合物（例如乙酸乙烯酯、顺式和反式二苯乙烯和环己烯）的反应。该反应以良好的收率得到相应的环丙烷衍生物、苯甲酰卡宾与烯属化合物双键的加成产物，以及顺式和反式二苯甲酰乙烯、二苯甲酰乙烷或双内酯。发现在顺式和反式二苯乙烯的情况下，卡宾的添加具有立体定向性。已经提出了一种机制，其中包含酮卡宾-金属螯合物作为反应中间体。
• Diastereoselective Reactions and Rearrangements of Chiral Allylic Sulfoximines
  作者：Stephen G. Pyne、Z. Dong、D. M. David、G. W. O'Meara

  DOI：10.1080/10426509708545524

  日期：1997.1.1

  nucleophilic and electrophilic chemistry of chiral allylic sulfominines and their alkyl sulfoximine counterparts are described including the synthesis of highly functionalised cyclopropanes derivatives. The synthesis of primary and secondary N-tosyl allylic amines via the palladium(0) catalysed rearrangement of allylic sulfoximines to allylic sulfinamides is also described.

  摘要：描述了手性烯丙基亚磺胺及其烷基亚砜亚胺对应物的亲核和亲电化学，包括高度官能化的环丙烷衍生物的合成。还描述了通过钯 (0) 催化的烯丙基亚砜亚胺重排为烯丙基亚磺酰胺的伯和仲 N-甲苯磺酰基烯丙基胺的合成。
• Stahl, Ingfried; Schomburg, Sabine; Kalinowski, Hans Otto, Chemische Berichte, 1984, vol. 117, # 6, p. 2247 - 2260
  作者：Stahl, Ingfried、Schomburg, Sabine、Kalinowski, Hans Otto

  DOI：——

  日期：——