ethyl 1,4-dimethylcyclohepta-1,3,5-triene-7-carboxylate | 1438848-30-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: ethyl 1,4-dimethylcyclohepta-1,3,5-triene-7-carboxylate
• 英文别名: ethyl 2,5-dimethyl-2,4,6-cycloheptatrienecarboxylate；Ethyl 2,5-dimethylcyclohepta-2,4,6-triene-1-carboxylate；ethyl 2,5-dimethylcyclohepta-2,4,6-triene-1-carboxylate
• CAS: 1438848-30-6
• 化学式: C₁₂H₁₆O₂
• 分子量: 192.258
• InChiKey: HVGBURNSNKXAFE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  重氮乙酸乙酯 、 对二甲苯 在 rhodium(II) trifluoroacetate 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以70%的产率得到ethyl 1,4-dimethylcyclohepta-1,3,5-triene-7-carboxylate
  参考文献：
  名称：

  Kinetic Separation and Asymmetric Reactions of Norcaradiene Cycloadducts: Facilitated Access via H₂O-Accelerated Cycloaddition

  摘要：

  We exploit the Buchner reaction to access 1,2-disubstituted cyclohexadiene synthons (norcaradienes), which participate in H2O-accelerated cycloaddition with dieneophiles to provide cyclopropyl-fused [2.2.2]-bicyclooctene derivatives in good yields. Regioisomeric mixtures can be kinetically separated by exploiting different reaction rates in Diels Alder reactions. Meso-Diels-Alder products may be enantioselectively desymmetrized, providing highly substituted cyclohexanes with up to seven contiguous stereocenters.

  DOI：

  10.1021/acs.orglett.5b03577

文献信息

• Büchner Reactions Catalyzed by a Silver(I) Pyridylpyrrolide: Understanding Arene C═C Insertion Selectivity
  作者：Nobuyuki Komine、Jaime A. Flores、Kuntal Pal、Kenneth G. Caulton、Daniel J. Mindiola

  DOI：10.1021/om301240d

  日期：2013.6.10

  The complex Ag-3(mu(2)-3,5-(CF3)(2)PyrPy)(3) (3,5-(CF3)(2)PyrPy = 2,2'-pyridylpyrrolide(1-) ligand) catalytically promotes the insertion of the carbene of ethyl diazoacetate (EDA), at room temperature, into the C=C bond of a series of arenes to ultimately ring-open them and form the corresponding cycloheptatrienes. In one case, the norcaradiene intermediate can be isolated, while regioselective C=C insertion can be promoted with certain arene substrates. The mechanism of C=C insertion, preference over C-H insertion, and origin of C=C regioselectivity has been probed by a combination of experimental and theoretical studies.
• Kinetic Separation and Asymmetric Reactions of Norcaradiene Cycloadducts: Facilitated Access via H₂O-Accelerated Cycloaddition
  作者：William D. Mackay、Jeffrey S. Johnson

  DOI：10.1021/acs.orglett.5b03577

  日期：2016.2.5

  We exploit the Buchner reaction to access 1,2-disubstituted cyclohexadiene synthons (norcaradienes), which participate in H2O-accelerated cycloaddition with dieneophiles to provide cyclopropyl-fused [2.2.2]-bicyclooctene derivatives in good yields. Regioisomeric mixtures can be kinetically separated by exploiting different reaction rates in Diels Alder reactions. Meso-Diels-Alder products may be enantioselectively desymmetrized, providing highly substituted cyclohexanes with up to seven contiguous stereocenters.