methyl (1R*,2R*,5R*,6R*)-5-methyl-7-oxobicyclo<4.3.0>non-3-en-2-carboxylate | 134360-97-7

• 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: methyl (1R*,2R*,5R*,6R*)-5-methyl-7-oxobicyclo<4.3.0>non-3-en-2-carboxylate
• 英文别名: methyl (3aS,4R,7S,7aS)-7-methyl-1-oxo-2,3,3a,4,7,7a-hexahydroindene-4-carboxylate
• CAS: 134360-97-7
• 化学式: C₁₂H₁₆O₃
• 分子量: 208.257
• InChiKey: LUTACTWRBNOMTB-SJQPAMGKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  山梨酸甲酯 、 2-环戊烯酮 以 二氯甲烷 为溶剂， 70.0 ℃ 、1399.99 MPa 条件下， 反应 48.0h， 以20%的产率得到methyl (1R*,2R*,5R*,6R*)-5-methyl-7-oxobicyclo<4.3.0>non-3-en-2-carboxylate
  参考文献：
  名称：

  Diels-Alder cycloadditions of electron-rich, electron-deficient, and push-pull dienes with cyclic dienophiles: high-pressure-induced reactions and theoretical calculations

  摘要：

  High-pressure-promoted (4 + 2) cycloadditions of cyclic dienophiles (mainly beta-angelica lactone and cyclopentenone) with electron-rich and push-pull hetero-substituted dienes have been investigated. Only one regio- and stereoisomer was obtained in all cases. While these dienophiles reacted smoothly with alkoxy- and (silyloxy)butadiene derivatives, replacement of oxygen by sulfur resulted in a dramatic decrease in the reactivity of the dienes. On the other hand, push-pull dienes exhibited reactivity similar to that of the electron-rich dienes, in that the dienophilicity was not changed substantially by the influence of an electron-withdrawing group. Theoretical calculations of activation enthalpies have been carried out by the semiempirical AM1 method. These values and frontier orbital considerations have permitted us to interpret the experimental results and to establish a relative order of reactivity of the dienes and dienophiles herein studied.

  DOI：

  10.1021/jo00013a012

文献信息

• Diels-Alder cycloadditions of electron-rich, electron-deficient, and push-pull dienes with cyclic dienophiles: high-pressure-induced reactions and theoretical calculations
  作者：Vicenc Branchadell、Mariona Sodupe、Rosa M. Ortuno、Antonio Oliva、Domingo Gomez-Pardo、Andre Guingant、Jean D'Angelo

  DOI：10.1021/jo00013a012

  日期：1991.6

  High-pressure-promoted (4 + 2) cycloadditions of cyclic dienophiles (mainly beta-angelica lactone and cyclopentenone) with electron-rich and push-pull hetero-substituted dienes have been investigated. Only one regio- and stereoisomer was obtained in all cases. While these dienophiles reacted smoothly with alkoxy- and (silyloxy)butadiene derivatives, replacement of oxygen by sulfur resulted in a dramatic decrease in the reactivity of the dienes. On the other hand, push-pull dienes exhibited reactivity similar to that of the electron-rich dienes, in that the dienophilicity was not changed substantially by the influence of an electron-withdrawing group. Theoretical calculations of activation enthalpies have been carried out by the semiempirical AM1 method. These values and frontier orbital considerations have permitted us to interpret the experimental results and to establish a relative order of reactivity of the dienes and dienophiles herein studied.