6-acetoxy-1,4-dimethylbicyclo<3.2.0>hept-3-ene | 133700-23-9

• 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: 6-acetoxy-1,4-dimethylbicyclo<3.2.0>hept-3-ene
• CAS: 133700-23-9
• 化学式: C₁₁H₁₆O₂
• 分子量: 180.247
• InChiKey: OFEFROKNSLNBFH-KHUXNXPUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.29
• 重原子数：
  13.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  6-acetoxy-1,4-dimethylbicyclo<3.2.0>hept-3-ene 在 四氧化锇 、 N-甲基吗啉氧化物 作用下， 以 水 、 丙酮 、 叔丁醇 为溶剂， 反应 24.0h， 以83%的产率得到6-acetoxy-1,4-dimethylbicyclo<3.2.0>heptane-3,4-diol
  参考文献：
  名称：

  Convenient method for the synthesis of lineatin, a pheromone component of Trypodendron lineatum

  摘要：

  Synthesis of racemic lineatin (1), a pheromone component of Trypodendron lineatum, is described. Condensation of 5-methyl-5-hexen-2-one (2) and triethyl phosphonoacetate with LiN(SiMe3)2 gave esters 3, which upon hydrolysis gave acids 4a-f. The bicyclo[3.2.0] ring compounds 5 and 6 were obtained via an intramolecular [2 + 2] addition by refluxing underivatized carboxylic acids 4a-f with NaOAc and Ac2O. Compound 5 was isomerized to the thermodynamically more stable isomer 6 using a Pd/C catalyst activated with hydrogen. Reduction of 6 with LiAlH4 gave the endo and exo isomers 7a and 7b (4:1). Isolation of the alcohol 7a followed by acetylation gave 8. Subsequent oxidation with OsO4 and methylmorpholine N-oxide gave diol 9. Cleavage of 9 with H5IO6 in diethyl ether gave keto aldehyde 10, which was converted to keto acetal 11. Treatment of 11 with MeMgBr followed by acidic workup gave 1. The overall efficiency is approximately 20%.

  DOI：

  10.1021/jo00010a033
• 作为产物：
  描述：

  乙酸酐 、 endo-1,4-dimethylbicyclo<3.2.0>hept-3-en-6-ol 在 吡啶 作用下， 以98%的产率得到6-acetoxy-1,4-dimethylbicyclo<3.2.0>hept-3-ene
  参考文献：
  名称：

  Convenient method for the synthesis of lineatin, a pheromone component of Trypodendron lineatum

  摘要：

  Synthesis of racemic lineatin (1), a pheromone component of Trypodendron lineatum, is described. Condensation of 5-methyl-5-hexen-2-one (2) and triethyl phosphonoacetate with LiN(SiMe3)2 gave esters 3, which upon hydrolysis gave acids 4a-f. The bicyclo[3.2.0] ring compounds 5 and 6 were obtained via an intramolecular [2 + 2] addition by refluxing underivatized carboxylic acids 4a-f with NaOAc and Ac2O. Compound 5 was isomerized to the thermodynamically more stable isomer 6 using a Pd/C catalyst activated with hydrogen. Reduction of 6 with LiAlH4 gave the endo and exo isomers 7a and 7b (4:1). Isolation of the alcohol 7a followed by acetylation gave 8. Subsequent oxidation with OsO4 and methylmorpholine N-oxide gave diol 9. Cleavage of 9 with H5IO6 in diethyl ether gave keto aldehyde 10, which was converted to keto acetal 11. Treatment of 11 with MeMgBr followed by acidic workup gave 1. The overall efficiency is approximately 20%.

  DOI：

  10.1021/jo00010a033