Methyl (1β,4β,5α,6β)-4-<<1-(methoxycarbonyl)ethenyl>oxy>-5-hydroxy-7-oxabicyclo<4.1.0>hept-2-ene-2-carboxylate

• 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 (1β,4β,5α,6β)-4-<<1-(methoxycarbonyl)ethenyl>oxy>-5-hydroxy-7-oxabicyclo<4.1.0>hept-2-ene-2-carboxylate
• 英文别名: Cyathiformine A；methyl (1R,4R,5S,6S)-5-hydroxy-4-(3-methoxy-3-oxoprop-1-en-2-yl)oxy-7-oxabicyclo[4.1.0]hept-2-ene-2-carboxylate
• 化学式: C₁₂H₁₄O₇
• 分子量: 270.239
• InChiKey: XDDVCQKECCSPCY-RGOKHQFPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  94.6
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  Methyl (1β,4β,5α,6β)-4-<<1-(methoxycarbonyl)ethenyl>oxy>-5-hydroxy-7-oxabicyclo<4.1.0>hept-2-ene-2-carboxylate 在 吡啶 作用下， 以 氘代苯 、 苯 为溶剂， 反应 3.0h， 生成 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：

  dimethyl chlorismate 在 碳酸氢钠 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以63%的产率得到Methyl (1β,4β,5α,6β)-4-<<1-(methoxycarbonyl)ethenyl>oxy>-5-hydroxy-7-oxabicyclo<4.1.0>hept-2-ene-2-carboxylate
  参考文献：
  名称：

  Total synthesis of (.+-.)-(1.beta.,6.alpha.,9.beta.,10.alpha.)-9-chloro-10-hydroxy-8-(methoxycarbonyl)-4-methylene-2,5-dioxabicyclo[4.4.0]dec-7-en-3-one, the first chloride-containing chorismate metabolite from fungi

  摘要：

  DOI：

  10.1021/jo00076a069

文献信息

• Synthesis of cyathiformines A-C: Unusual fungal metabolites derived from chorismic acid
  作者：Rose-Marie Meier、Bruce Ganem

  DOI：10.1016/s0040-4020(01)86987-8

  日期：1994.2

  Expeditious syntheses of the title compounds are reported which lend credence to the apparent biogenetic relationship between the cyathiformines and (-)-chorismic acid.
• Cyathiformines A–D, new chorismate-derived metabolites from the fungus clitocybe cyathiformis
  作者：Alberto Arnone、Rosanna Cardillo、Gianluca Nasini、Orso Vajna de Pava

  DOI：10.1016/s0040-4020(01)87202-1

  日期：1993.8

  Cyathiformines A-D, 1, 4a, 5 and 6a, have been isolated from the Basidiomycetous fungus Clitocybe cyathiformis. Structural determination was based on NMR studies and chemical evidence.
• Total synthesis of (.+-.)-(1.beta.,6.alpha.,9.beta.,10.alpha.)-9-chloro-10-hydroxy-8-(methoxycarbonyl)-4-methylene-2,5-dioxabicyclo[4.4.0]dec-7-en-3-one, the first chloride-containing chorismate metabolite from fungi
  作者：Cheng Tu、Glenn A. Berchtold

  DOI：10.1021/jo00076a069

  日期：1993.11
• 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.