3-(4-nitrophenyl)-3-phenylcyclopentene | 139952-08-2

• 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: 3-(4-nitrophenyl)-3-phenylcyclopentene
• 英文别名: 1-Nitro-4-(1-phenylcyclopent-2-en-1-yl)benzene
• CAS: 139952-08-2
• 化学式: C₁₇H₁₅NO₂
• 分子量: 265.312
• InChiKey: KWOVLIHVQNEEEM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  45.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-(4-nitrophenyl)-3-phenylcyclopentene 在 sodium tetrahydroborate 、 tin(ll) chloride 作用下， 以 乙醇 为溶剂， 反应 0.5h， 以78%的产率得到3-(4-aminophenyl)-3-phenylcyclopentene
  参考文献：
  名称：

  Evidence of stereoelectronic control in osmium-catalyzed cis-dihydroxylations of sterically unbiased 3,3-diarylcyclopentenes

  摘要：

  This study provides strong evidence for the stereoelectronic control of diastereoselectivity in the osmium tetraoxide-catalyzed cis-dihydroxylation of sterically unbiased 3-(4-X-phenyl)-3-phenylcyclopentenes 1 (X = NO2, Br, Cl, OCH3, N(CH3)2), producing diastereomeric cis-diols 2 in cis:trans ratios (diol relative to the substituted arene) varying from 70:30 to 36:64 as determined by H-1 NMR and C-13 NMR spectroscopy. The reactions were carried out at room temperature in an 8:1 acetone/water solvent system, utilizing trimethylamine N-oxide as the terminal oxidant. Structural assignments were made by 2D-NOE H-1 NMR spectroscopy, C-13 NMR spectroscopy, and X-ray crystallographic analysis. In all cases the addition occurred opposite the more electron-rich aromatic ring as predicted by Cieplak's theory for explaining stereoelectronic control. The observed ratios correspond to an overall energy difference of 1.1 kcal/mol. A Hammet plot of log (cis:trans) versus the sigma(p), parameter produced a linear relationship with a correlation coefficient of 0.97. An efficient synthesis of the diarylcyclopentenes is described. The diastereomeric diols, or derivatives thereof, were separable by preparatory thin-layer chromatography.

  DOI：

  10.1021/ja00029a029
• 作为产物：
  描述：

  2-(4-nitrophenyl)-2-phenylcyclopentanone tosylhydrazone 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 18.0h， 以66%的产率得到3-(4-nitrophenyl)-3-phenylcyclopentene
  参考文献：
  名称：

  Evidence of stereoelectronic control in osmium-catalyzed cis-dihydroxylations of sterically unbiased 3,3-diarylcyclopentenes

  摘要：

  This study provides strong evidence for the stereoelectronic control of diastereoselectivity in the osmium tetraoxide-catalyzed cis-dihydroxylation of sterically unbiased 3-(4-X-phenyl)-3-phenylcyclopentenes 1 (X = NO2, Br, Cl, OCH3, N(CH3)2), producing diastereomeric cis-diols 2 in cis:trans ratios (diol relative to the substituted arene) varying from 70:30 to 36:64 as determined by H-1 NMR and C-13 NMR spectroscopy. The reactions were carried out at room temperature in an 8:1 acetone/water solvent system, utilizing trimethylamine N-oxide as the terminal oxidant. Structural assignments were made by 2D-NOE H-1 NMR spectroscopy, C-13 NMR spectroscopy, and X-ray crystallographic analysis. In all cases the addition occurred opposite the more electron-rich aromatic ring as predicted by Cieplak's theory for explaining stereoelectronic control. The observed ratios correspond to an overall energy difference of 1.1 kcal/mol. A Hammet plot of log (cis:trans) versus the sigma(p), parameter produced a linear relationship with a correlation coefficient of 0.97. An efficient synthesis of the diarylcyclopentenes is described. The diastereomeric diols, or derivatives thereof, were separable by preparatory thin-layer chromatography.

  DOI：

  10.1021/ja00029a029

文献信息

• Evidence for stereoelectronic control in the epoxidation of sterically unbiased 3,3-diarylcyclopentenes
  作者：Ronald L. Halterman、Marjorie A. McEvoy

  DOI：10.1016/s0040-4039(00)77707-0

  日期：1992.2

  Epoxidations of the sterically unbiased olefin, 3-(4-X-phenyl)-3-phenylcyclopentene (X = NO2, Br, Cl, OCH3) with peracetic acid have been found to proceed with up to 73:27 stereoselectivity. Stereochemistry of the products was determined by lanthanide shift studies, COSY and 1D NOE1H NMR spectroscopic techniques and chemical correlation to the known 2,2-diarylcyclopentanols.

  已经发现，用过乙酸对空间无偏烯烃3-（4-X-苯基）-3-苯基环戊烯（X = NO 2，Br，Cl，OCH 3）进行环氧化，其立体选择性高达73:27。通过镧系元素转移研究，COZY和1D NOE 1 H NMR光谱技术以及与已知的2,2-二芳基环戊醇的化学相关性确定了产物的立体化学。
• Evidence of stereoelectronic control in osmium-catalyzed cis-dihydroxylations of sterically unbiased 3,3-diarylcyclopentenes
  作者：Ronald L. Halterman、Marjorie A. McEvoy

  DOI：10.1021/ja00029a029

  日期：1992.1

  This study provides strong evidence for the stereoelectronic control of diastereoselectivity in the osmium tetraoxide-catalyzed cis-dihydroxylation of sterically unbiased 3-(4-X-phenyl)-3-phenylcyclopentenes 1 (X = NO2, Br, Cl, OCH3, N(CH3)2), producing diastereomeric cis-diols 2 in cis:trans ratios (diol relative to the substituted arene) varying from 70:30 to 36:64 as determined by H-1 NMR and C-13 NMR spectroscopy. The reactions were carried out at room temperature in an 8:1 acetone/water solvent system, utilizing trimethylamine N-oxide as the terminal oxidant. Structural assignments were made by 2D-NOE H-1 NMR spectroscopy, C-13 NMR spectroscopy, and X-ray crystallographic analysis. In all cases the addition occurred opposite the more electron-rich aromatic ring as predicted by Cieplak's theory for explaining stereoelectronic control. The observed ratios correspond to an overall energy difference of 1.1 kcal/mol. A Hammet plot of log (cis:trans) versus the sigma(p), parameter produced a linear relationship with a correlation coefficient of 0.97. An efficient synthesis of the diarylcyclopentenes is described. The diastereomeric diols, or derivatives thereof, were separable by preparatory thin-layer chromatography.