2-Diazo-4-[2-(4-methoxy-phenyl)-ethyl]-3-oxo-heptanoic acid methyl ester | 200408-95-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 2-Diazo-4-[2-(4-methoxy-phenyl)-ethyl]-3-oxo-heptanoic acid methyl ester
• 英文别名: Methyl 2-diazo-4-[2-(4-methoxyphenyl)ethyl]-3-oxoheptanoate
• CAS: 200408-95-3
• 化学式: C₁₇H₂₂N₂O₄
• 分子量: 318.373
• InChiKey: AVMLZUPMAIZQOX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  23
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  86.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-Diazo-4-[2-(4-methoxy-phenyl)-ethyl]-3-oxo-heptanoic acid methyl ester 在 rhodium(II) acetate dimer 作用下， 以 二氯甲烷 为溶剂， 生成 (1R,5S)-5-(4-Methoxy-phenyl)-2-oxo-3-propyl-cyclopentanecarboxylic acid methyl ester 、 (1R,5S)-3-[2-(4-Methoxy-phenyl)-ethyl]-5-methyl-2-oxo-cyclopentanecarboxylic acid methyl ester
  参考文献：
  名称：

  Electronic Effects of Rh(II)-Mediated Carbenoid Intramolecular C−H Insertion:  A Linear Free Energy Correlation Study

  摘要：

  The relative rates of the Rh(II)-mediated carbenoid insertion into the benzylic C-H bonds of a series of para-substituted phenyl substrates have been measured by an indirect intramolecular competition method. Three catalysts, rhodium(II) acetate, rhodium(II) trifluoroacetate, and rhodium(II) acetamide, were investigated. The effect of solvent was also studied on the reactions with rhodium(II) acetate as catalyst. The relative rates were analyzed by the Hammett equation. The relative rates are found to correlate better with sigma than with sigma(+) for all three catalysts when CH2Cl2 is the solvent. For the insertion reactions catalyzed by Rh-2(OAc)(4), Rh-2(O2CCF3)(4), and Rh-2(acam)(4) in CH2Cl2, the Hammett correlations of the relative rates with a give reaction constants of -1.26 (r = 0.98), -0.66 (r = 0.97), and -1.39 (r = 0.98), respectively. The Hammett analysis also indicates no significant solvent effect. The mechanistic significance of these Hammett correlations is discussed.

  DOI：

  10.1021/jo971747j
• 作为产物：
  描述：

  4-[2-(4-Methoxy-phenyl)-ethyl]-3-oxo-heptanoic acid methyl ester 在 对甲苯磺酰叠氮 、 三乙胺 作用下， 以 乙腈 为溶剂， 反应 6.0h， 以80%的产率得到2-Diazo-4-[2-(4-methoxy-phenyl)-ethyl]-3-oxo-heptanoic acid methyl ester
  参考文献：
  名称：

  Electronic Effects of Rh(II)-Mediated Carbenoid Intramolecular C−H Insertion:  A Linear Free Energy Correlation Study

  摘要：

  The relative rates of the Rh(II)-mediated carbenoid insertion into the benzylic C-H bonds of a series of para-substituted phenyl substrates have been measured by an indirect intramolecular competition method. Three catalysts, rhodium(II) acetate, rhodium(II) trifluoroacetate, and rhodium(II) acetamide, were investigated. The effect of solvent was also studied on the reactions with rhodium(II) acetate as catalyst. The relative rates were analyzed by the Hammett equation. The relative rates are found to correlate better with sigma than with sigma(+) for all three catalysts when CH2Cl2 is the solvent. For the insertion reactions catalyzed by Rh-2(OAc)(4), Rh-2(O2CCF3)(4), and Rh-2(acam)(4) in CH2Cl2, the Hammett correlations of the relative rates with a give reaction constants of -1.26 (r = 0.98), -0.66 (r = 0.97), and -1.39 (r = 0.98), respectively. The Hammett analysis also indicates no significant solvent effect. The mechanistic significance of these Hammett correlations is discussed.

  DOI：

  10.1021/jo971747j