Dimethyl 4-oxo-1-(3-butenyl)-8-oxabicyclo<3.2.1>oct-6-ene-6,7-dicarboxylate | 143888-27-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: Dimethyl 4-oxo-1-(3-butenyl)-8-oxabicyclo<3.2.1>oct-6-ene-6,7-dicarboxylate
• 英文别名: Dimethyl 1-but-3-enyl-4-oxo-8-oxabicyclo[3.2.1]oct-6-ene-6,7-dicarboxylate
• CAS: 143888-27-1
• 化学式: C₁₅H₁₈O₆
• 分子量: 294.304
• InChiKey: RNXMMLRBDYQNMB-UHFFFAOYSA-N

物化性质

• 沸点：
  399.5±42.0 °C(Predicted)
• 密度：
  1.250±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 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：

  methyl 4-oxooct-7-enoate 在 rhodium(II) acetate dimer 作用下， 以 苯 为溶剂， 反应 6.0h， 生成 Dimethyl 4-oxo-1-(3-butenyl)-8-oxabicyclo<3.2.1>oct-6-ene-6,7-dicarboxylate
  参考文献：
  名称：

  Tandem cyclization-cycloaddition reaction of rhodium carbenoids. Studies dealing with intramolecular cycloadditions

  摘要：

  A series of 5-alkenyl-1-diazo-2,5-pentanediones, when treated with a catalytic quantity of rhodium(II) acetate, were found to give cycloadducts derived from the intramolecular trapping of a carbonyl ylide intermediate. Tethers of three or four methylenes readily enter into intramolecular cycloaddition, while longer and shorter tethers were reluctant to do so. Alkenes attached to the formally cationic terminus of the carbonyl ylide readily undergo internal cycloaddition if the tether allows for a relatively strain-free transition state. The internal cycloaddition reaction does not occur when the olefinic side chain is attached by means of an ester functionality. Bimolecular trapping experiments established that carbonyl ylide formation occurred, but the dipole does not undergo intramolecular cycloaddition. The inability of these alpha-diazo keto esters to undergo internal cycloaddition is related to conformational factors. The equilibrium between the two possible conformations of the dipole lies predominantly on the side of the Z-isomer. In this orientation, intramolecular dipolar cycloaddition cannot occur, and instead the dipole collapses by means of a proton transfer to give an enol ether.

  DOI：

  10.1021/jo00047a032

文献信息

• Tandem cyclization-cycloaddition reaction of rhodium carbenoids. Studies dealing with intramolecular cycloadditions
  作者：Albert Padwa、Susan F. Hornbuckle、Glen E. Fryxell、Zhijia J. Zhang

  DOI：10.1021/jo00047a032

  日期：1992.10

  A series of 5-alkenyl-1-diazo-2,5-pentanediones, when treated with a catalytic quantity of rhodium(II) acetate, were found to give cycloadducts derived from the intramolecular trapping of a carbonyl ylide intermediate. Tethers of three or four methylenes readily enter into intramolecular cycloaddition, while longer and shorter tethers were reluctant to do so. Alkenes attached to the formally cationic terminus of the carbonyl ylide readily undergo internal cycloaddition if the tether allows for a relatively strain-free transition state. The internal cycloaddition reaction does not occur when the olefinic side chain is attached by means of an ester functionality. Bimolecular trapping experiments established that carbonyl ylide formation occurred, but the dipole does not undergo intramolecular cycloaddition. The inability of these alpha-diazo keto esters to undergo internal cycloaddition is related to conformational factors. The equilibrium between the two possible conformations of the dipole lies predominantly on the side of the Z-isomer. In this orientation, intramolecular dipolar cycloaddition cannot occur, and instead the dipole collapses by means of a proton transfer to give an enol ether.