dimethyl 1,4-epoxy-5-oxo-2-bicyclo<6.4.0>dodecene-2,3-dicarboxylate | 133374-56-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: dimethyl 1,4-epoxy-5-oxo-2-bicyclo<6.4.0>dodecene-2,3-dicarboxylate
• 英文别名: Dimethyl 9-oxo-13-oxatricyclo[8.2.1.01,6]tridec-11-ene-11,12-dicarboxylate
• CAS: 133374-56-8
• 化学式: C₁₆H₂₀O₆
• 分子量: 308.331
• InChiKey: CTAVERJWHGCVHA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  78.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  2-(4-diazo-3-oxobutyl)cyclohexanone 、 丁炔二酸二甲酯 在 dirhodium tetraacetate 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以50%的产率得到dimethyl 1,4-epoxy-5-oxo-2-bicyclo<6.4.0>dodecene-2,3-dicarboxylate
  参考文献：
  名称：

  Tandem cyclization-cycloaddition reaction of rhodium carbenoids. Studies dealing with the geometric requirements of dipole formation

  摘要：

  The carbenoid intermediate derived by the treatment of several 1-diazobutanediones with rhodium(II) acetate undergoes ready transannular cyclization onto the neighboring keto group to give five-membered ring carbonyl ylides. The dipole derived from ethyl 4-diazo-2-methyl-3-oxobutyrate was found to undergo a rapid proton transfer, producing 5-ethoxy-4-methyl-3-(2H)-furanone. When the position adjacent to the diazo carbonyl group is blocked with two substituent groups, however, smooth 1,3-dipolar cycloaddition occurs. The observed regioselectivity can be nicely accommodated in terms of frontier molecular orbital (FMO) theory. A type II FMO interaction is involved since carbonyl ylides possess one of the smallest HOMO-LUMO energy gaps of common 1,3-dipoles. The rhodium(II)-catalyzed reaction of 1-diazo-6-phenyl-2,6-hexanedione afforded a mixture of products. In addition to the expected cycloadduct, a product derived from the bimolecular addition of the rhodium carbenoid to benzene was obtained. The formation of a mixture of products in this case suggests that entropic factors have sufficiently retarded the rate of intramolecular cyclization so as to allow the bimolecular reaction with benzene to occur. No observable cycloadduct was obtained from the diazohexanedione system, thereby indicating that the longer tether was sufficient to shut down dipole formation.

  DOI：

  10.1021/jo00010a019

文献信息

• Tandem cyclization-cycloaddition reaction of rhodium carbenoids. Studies dealing with the geometric requirements of dipole formation
  作者：Albert Padwa、Richard L. Chinn、Susan F. Hornbuckle、Zhijia J. Zhang

  DOI：10.1021/jo00010a019

  日期：1991.5

  The carbenoid intermediate derived by the treatment of several 1-diazobutanediones with rhodium(II) acetate undergoes ready transannular cyclization onto the neighboring keto group to give five-membered ring carbonyl ylides. The dipole derived from ethyl 4-diazo-2-methyl-3-oxobutyrate was found to undergo a rapid proton transfer, producing 5-ethoxy-4-methyl-3-(2H)-furanone. When the position adjacent to the diazo carbonyl group is blocked with two substituent groups, however, smooth 1,3-dipolar cycloaddition occurs. The observed regioselectivity can be nicely accommodated in terms of frontier molecular orbital (FMO) theory. A type II FMO interaction is involved since carbonyl ylides possess one of the smallest HOMO-LUMO energy gaps of common 1,3-dipoles. The rhodium(II)-catalyzed reaction of 1-diazo-6-phenyl-2,6-hexanedione afforded a mixture of products. In addition to the expected cycloadduct, a product derived from the bimolecular addition of the rhodium carbenoid to benzene was obtained. The formation of a mixture of products in this case suggests that entropic factors have sufficiently retarded the rate of intramolecular cyclization so as to allow the bimolecular reaction with benzene to occur. No observable cycloadduct was obtained from the diazohexanedione system, thereby indicating that the longer tether was sufficient to shut down dipole formation.