Dimethyl epoxypyruvoylchorismate | 157405-18-0

• 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: Dimethyl epoxypyruvoylchorismate
• 英文别名: methyl (1R,4R,5S,6R)-4-(3-methoxy-3-oxoprop-1-en-2-yl)oxy-5-(2-oxopropanoyloxy)-7-oxabicyclo[4.1.0]hept-2-ene-2-carboxylate
• CAS: 157405-18-0
• 化学式: C₁₅H₁₆O₉
• 分子量: 340.287
• InChiKey: LGLLWDOFCFYNTR-WISYIIOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  24
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  118
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  Dimethyl epoxypyruvoylchorismate 以 氘代苯 为溶剂， 反应 2.0h， 以77%的产率得到dimethyl (1R,3R,6S,9S,10R,12R)-6-methyl-7-oxo-2,5,8,11-tetraoxatetracyclo[7.5.0.03,6.010,12]tetradec-13-ene-3,13-dicarboxylate
  参考文献：
  名称：

  An Approach to 6-Oxygenated Shikimic Acid Derivatives by Photolysis of the Pyruvate Ester of Dimethyl Epoxychorismate

  摘要：

  We report an unusual rearrangement of a synthetic epoxychorismic acid derivative which provides access to the 6-substituted shikimic acid framework. Photolysis of the pyruvate ester of dimethyl epoxychorismate triggered an intramolecular Paterno-Buchi photocyclization of the enol pyruvate alkene and the ketone group of the pyruvate ester, leading to a 2,2,3,3-tetrasubstituted oxetane ring. Upon standing for 1 week in CDCl3 or in the presence of CF3CO2D, the primary photoproduct underwent a slow epoxide-opening reaction with participation by the oxetane-substituted carbomethoxy group to form an unusual fused tetracyclic lactone. The chemistry described here suggests at least one plausible pathway, with appropriate stereoelectronic constraints, by which oxidation of shikimic acid at C6 might be achieved.

  DOI：

  10.1021/jo00097a055
• 作为产物：
  描述：

  Epoxychorismic acid 在 吡啶 作用下， 以 甲醇 、 乙醚 、 苯 为溶剂， 反应 2.5h， 生成 Dimethyl epoxypyruvoylchorismate
  参考文献：
  名称：

  An Approach to 6-Oxygenated Shikimic Acid Derivatives by Photolysis of the Pyruvate Ester of Dimethyl Epoxychorismate

  摘要：

  We report an unusual rearrangement of a synthetic epoxychorismic acid derivative which provides access to the 6-substituted shikimic acid framework. Photolysis of the pyruvate ester of dimethyl epoxychorismate triggered an intramolecular Paterno-Buchi photocyclization of the enol pyruvate alkene and the ketone group of the pyruvate ester, leading to a 2,2,3,3-tetrasubstituted oxetane ring. Upon standing for 1 week in CDCl3 or in the presence of CF3CO2D, the primary photoproduct underwent a slow epoxide-opening reaction with participation by the oxetane-substituted carbomethoxy group to form an unusual fused tetracyclic lactone. The chemistry described here suggests at least one plausible pathway, with appropriate stereoelectronic constraints, by which oxidation of shikimic acid at C6 might be achieved.

  DOI：

  10.1021/jo00097a055

文献信息

• An Approach to 6-Oxygenated Shikimic Acid Derivatives by Photolysis of the Pyruvate Ester of Dimethyl Epoxychorismate
  作者：Rose-Marie Meier、Bruce Ganem

  DOI：10.1021/jo00097a055

  日期：1994.9

  We report an unusual rearrangement of a synthetic epoxychorismic acid derivative which provides access to the 6-substituted shikimic acid framework. Photolysis of the pyruvate ester of dimethyl epoxychorismate triggered an intramolecular Paterno-Buchi photocyclization of the enol pyruvate alkene and the ketone group of the pyruvate ester, leading to a 2,2,3,3-tetrasubstituted oxetane ring. Upon standing for 1 week in CDCl3 or in the presence of CF3CO2D, the primary photoproduct underwent a slow epoxide-opening reaction with participation by the oxetane-substituted carbomethoxy group to form an unusual fused tetracyclic lactone. The chemistry described here suggests at least one plausible pathway, with appropriate stereoelectronic constraints, by which oxidation of shikimic acid at C6 might be achieved.