1,1-diphenyl-(2-p-trifluorophenyl)cyclopropane

• 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: 1,1-diphenyl-(2-p-trifluorophenyl)cyclopropane
• 英文别名: (2-(4-(trifluoromethyl)phenyl)cyclopropane-1,1-diyl)dibenzene；1-(2,2-Diphenylcyclopropyl)-4-(trifluoromethyl)benzene
• 化学式: C₂₂H₁₇F₃
• 分子量: 338.372
• InChiKey: PMGRNXSEYDRBAO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.6
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  二苯甲酮 在 亚碘酰苯 、 对甲苯磺酸 、 一水合肼 、 nickel(II) hydroxide 作用下， 以 水 为溶剂， 反应 1.0h， 生成 1,1-diphenyl-(2-p-trifluorophenyl)cyclopropane
  参考文献：
  名称：

  的高价碘（III）氧化为重氮化合物和一锅镍（II）催化的环丙烷化

  摘要：

  描述了用未取代的酮对各种烯烃进行催化环丙烷化的一锅法。发现碘代苯（PhIO ）是到重氮化合物的有效氧化剂。选择Ni（OH）2作为有效且廉价的金属催化剂。在温和（80°C）和纯净的条件下，可以以中等到良好的收率（42–91％）有效地产生环丙烷产物（5分钟至4小时）。

  DOI：

  10.1039/c5nj02378e

文献信息

• Stable group 8 metal porphyrin mono- and bis(dialkylcarbene) complexes: synthesis, characterization, and catalytic activity
  作者：Hai-Xu Wang、Qingyun Wan、Kam-Hung Low、Cong-Ying Zhou、Jie-Sheng Huang、Jun-Long Zhang、Chi-Ming Che

  DOI：10.1039/c9sc05432d

  日期：——

  (CHR or CR2, R = alkyl) complexes have been extensively studied for alkylcarbene (CHR) ligands coordinated with high-valent early transition metal ions (a.k.a. Schrock carbenes or alkylidenes), yet dialkylcarbene (CR2) complexes remain less developed with bis(dialkylcarbene) species being little (if at all) explored. Herein, several group 8 metal porphyrin dialkylcarbene complexes, including Fe- and R

  烷基取代卡宾（CHR 或 CR 2，R = 烷基）配合物已被广泛研究用于与高价早期过渡金属离子（又名 Schrock 卡宾或亚烷基）配位的烷基卡宾（CHR）配体，但二烷基卡宾（CR 2）配合物仍然存在不太发达，双（二烷基卡宾）物种很少（如果有的话）被探索。本文中，几种第8族金属卟啉二烷基卡宾络合物，包括Fe-和Ru-单(二烷基卡宾)络合物[M(Por)(Ad)]( 1a,b，M=Fe，Por=卟啉二价阴离子，Ad=2-金刚烷基；合成了 2a,b , M = Ru) 和 Os-双(二烷基碳烯) 配合物 [Os(Por)(Ad) 2 ] ( 3a–c ) 并进行了晶体学表征。对它们的电子结构的详细研究表明，这些配合物本质上是低价的 M( II )-卡宾。这些配合物表现出显着的热稳定性和化学惰性，这是通过强金属卡宾共价性、超共轭性和刚性金刚形卡宾骨架的协同效应合理化的。各种光谱技术和 DFT 计算表明，二烷基卡宾
• Isolation and X-ray Crystal Structure of an Unusual Biscarbene Metal Complex and Its Reactivity toward Cyclopropanation and Allylic C−H Insertion of Unfunctionalized Alkenes
  作者：Yan Li、Jie-Sheng Huang、Zhong-Yuan Zhou、Chi-Ming Che

  DOI：10.1021/ja003184q

  日期：2001.5.1
• Discrete Bridging and Terminal Copper Carbenes in Copper-Catalyzed Cyclopropanation
  作者：Xuliang Dai、Timothy H. Warren

  DOI：10.1021/ja047935q

  日期：2004.8.1

  The Cu(I) beta-diketiminate [Me2NN]Cu(eta(2)-ethylene) (2) catalyzes the cyclopropanation of styrene with N2CPh2 to give 1,1,2-triphenylcyclopropane in 67% yield. Addition of N2CPh2 to 2 equiv of 2 allows for the isolation of the dicopper carbene [Me2NN]Cu}(2)(mu-CPh2) (3) in which the diphenylcarbene moiety is symmetrically bound between two [Me2NN]Cu fragments (Cu-C = 1.922(4) and 1.930(4) Angstrom) with a Cu-Cu separation of 2.4635(7) Angstrom. In toluene-d(8) solution, 3 reversibly dissociates a [Me2NN]Cu fragment to give [Me2NN]Cu(toluene) and the terminal carbene [Me2NN]Cu=CPh2. Dicopper carbene 3 reacts with 3 equiv of styrene to give 1,1,2-triphenylcyclopropane and 2 equiv of [Me2NN]Cu(eta(2)-styrene) within minutes. DFT studies with simplified ligands indicate a stronger Cu-C pi-back-bonding interaction from two Cu(I) centers to the carbene acceptor orbital in a dicopper carbene than that present in a monocopper carbene. Nonetheless, the terminal carbene [Me3NN]Cu=CPh2 (8) that possesses a p-methyl group on each beta-diketiminato N-aryl ring may be isolated and exhibits a shortened Cu-C distance of 1.834(3) Angstrom. The stoichiometric cyclopropanation of styrene by 8 in 1,4-dioxane is first-order in both copper carbene 8 and styrene with activation parameters DeltaH(not similar or equal to) = 10.4(3) kcal/mol and DeltaS(not similar or equal to) = -32.3(9) cal/mol-K. In 1,4-dioxane, 8 decomposes to Ph2C=CPh2 via first-order kinetics with activation parameters DeltaH(not similar or equal to) = 21(1) kcal/mol and DeltaS(not similar or equal to) = -8(3) cal/mol-K. Arene solutions of thermally sensitive terminal carbene 8 decompose to [Me3NN]-Cu(arene), which reacts with 8 still present in solution to give the more thermally stable [Me3NN]Cu}(2)-(mu-CPh2).