methyl (1S,3aR,4S,7R,7aS,1'R,2'R,5'R)-1-[2'-(1''-formylvinyl)-5'-methylcyclopentylmethyl]-1-hydroxymethyl-3-isopropyl-3a,4,7,7a-tetrahydro-1H-4,7-methanoindene-2-carboxylate | 528878-74-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: methyl (1S,3aR,4S,7R,7aS,1'R,2'R,5'R)-1-[2'-(1''-formylvinyl)-5'-methylcyclopentylmethyl]-1-hydroxymethyl-3-isopropyl-3a,4,7,7a-tetrahydro-1H-4,7-methanoindene-2-carboxylate
• 英文别名: methyl (1S,2R,5S,6S,7R)-5-(hydroxymethyl)-5-[[(1R,2R,5R)-2-methyl-5-(3-oxoprop-1-en-2-yl)cyclopentyl]methyl]-3-propan-2-yltricyclo[5.2.1.02,6]deca-3,8-diene-4-carboxylate
• CAS: 528878-74-2
• 化学式: C₂₆H₃₆O₄
• 分子量: 412.569
• InChiKey: XKQKGOQMJDGGPU-UPMSUHOJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  30
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  63.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl (1S,3aR,4S,7R,7aS,1'R,2'R,5'R)-1-[2'-(1''-formylvinyl)-5'-methylcyclopentylmethyl]-1-hydroxymethyl-3-isopropyl-3a,4,7,7a-tetrahydro-1H-4,7-methanoindene-2-carboxylate 在 六甲基磷酰三胺 、 丙烷-1-硫醇 、 sodium hydride 作用下， 以 邻二氯苯 为溶剂， 反应 49.0h， 以17 mg的产率得到iso-sordaricin
  参考文献：
  名称：

  Total Synthesis of Sordaricin

  摘要：

  An enantioconvergent total synthesis of sordaricin (3), the diterpene aglycon of an important class of antifungal compounds, is described. Two approaches were explored, the first of which utilized a possible biogenetic intramolecular [4 + 2] cycloaddition to form the complete carbon skeleton of the target molecule as a single regioisomer 30. A second approach employed a tandem cycloreversion/intramolecular [4 + 2] cycloaddition process to afford not only the desired product 30 but also significant quantities of the undesired regioisomer iso-30. An investigation into the reasons for the difference in regioselectivity between these two reactions revealed the intervention of a cycloreversion/cycloaddition pathway at elevated temperatures leading to the formation of iso-30. Experimental evidence supports the hypothesis that iso-30 is the more thermodynamically stable of the two regioisomers.

  DOI：

  10.1021/jo048199b
• 作为产物：
  描述：

  methyl (1S,3aR,4S,7R,7aS,1'R,2'R,5'R)-3-hydroxy-1-methoxymethoxymethyl-1-[{2'-(1''-(methoxymethoxymethyl)vinyl)-5'-methylcyclopentyl}methyl]-3a,4,7,7a-tetrahydro-1H-4,7-methanoindene-2-carboxylate 在 manganese(IV) oxide 、 丁硫醇 、 sodium hydride 、 lithium,azanidylidenemethylidenecopper,2H-thiophen-2-ide 、 magnesium bromide 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 25.5h， 生成 methyl (1S,3aR,4S,7R,7aS,1'R,2'R,5'R)-1-[2'-(1''-formylvinyl)-5'-methylcyclopentylmethyl]-1-hydroxymethyl-3-isopropyl-3a,4,7,7a-tetrahydro-1H-4,7-methanoindene-2-carboxylate
  参考文献：
  名称：

  Total Synthesis of Sordaricin

  摘要：

  An enantioconvergent total synthesis of sordaricin (3), the diterpene aglycon of an important class of antifungal compounds, is described. Two approaches were explored, the first of which utilized a possible biogenetic intramolecular [4 + 2] cycloaddition to form the complete carbon skeleton of the target molecule as a single regioisomer 30. A second approach employed a tandem cycloreversion/intramolecular [4 + 2] cycloaddition process to afford not only the desired product 30 but also significant quantities of the undesired regioisomer iso-30. An investigation into the reasons for the difference in regioselectivity between these two reactions revealed the intervention of a cycloreversion/cycloaddition pathway at elevated temperatures leading to the formation of iso-30. Experimental evidence supports the hypothesis that iso-30 is the more thermodynamically stable of the two regioisomers.

  DOI：

  10.1021/jo048199b

文献信息

• Total Synthesis of Sordaricin
  作者：Lewis N. Mander、Regan J. Thomson

  DOI：10.1021/jo048199b

  日期：2005.3.1

  An enantioconvergent total synthesis of sordaricin (3), the diterpene aglycon of an important class of antifungal compounds, is described. Two approaches were explored, the first of which utilized a possible biogenetic intramolecular [4 + 2] cycloaddition to form the complete carbon skeleton of the target molecule as a single regioisomer 30. A second approach employed a tandem cycloreversion/intramolecular [4 + 2] cycloaddition process to afford not only the desired product 30 but also significant quantities of the undesired regioisomer iso-30. An investigation into the reasons for the difference in regioselectivity between these two reactions revealed the intervention of a cycloreversion/cycloaddition pathway at elevated temperatures leading to the formation of iso-30. Experimental evidence supports the hypothesis that iso-30 is the more thermodynamically stable of the two regioisomers.