(E)-β-ocimene | 36602-32-1

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: (E)-β-ocimene
• 英文别名: 2,6-dimethyl-2,5-octadien-7-yne；(3E)-3,7-Dimethyl-3,6-octadien-1-yne；(3E)-3,7-dimethylocta-3,6-dien-1-yne
• CAS: 36602-32-1
• 化学式: C₁₀H₁₄
• 分子量: 134.221
• InChiKey: AJUDLCRYEGKSIL-CSKARUKUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (E)-β-ocimene 、 alkaline earth salt of/the/ methylsulfuric acid 以 乙腈 为溶剂， 反应 3.5h， 以56%的产率得到2-((E)-2-Methoxy-propenyl)-3-methyl-4-(3-methyl-but-2-enyl)-cyclobut-2-enone
  参考文献：
  名称：

  Electronic Tuning of Fischer Carbene Complexes in the Preparation of Bicyclo[3.1.1]heptanones as Taxane A-ring Synthons

  摘要：

  A synthetic route to taxol and other Taxus diterpenes is described which employs as a key step the reaction between a Fischer carbene complex and a 1,6 enyne to construct 1-substituted-7,7-dimethyl-2-methylenebicyclo[3.1.1] heptan-6-ones. It was found that the reaction between complex 2 and 7-methyl-3-methylene-6-octen-1-yne (dienyne 30) yielded a mixture of bicyclo[3.1.1]heptanone 35 and cyclobutenone 36, the latter possibly arising from the migration of the chromium fragment from an electron-rich alkene to a less electron-rich alkene in the vinyl carbene complex intermediate (i.e. 40-42). On this basis, it was expected that bicycloheptanone yields would increase with increasing electron deficiency in the intermediate 40 since this should lead to more competitive CO insertion. This was observed with a series of electronically modified carbene complexes (45 and 48a-d). The more electron deficient complexes gave good yields of bicycloheptanones, thus providing an efficient means for preparing taxane A-ring synthons. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(99)01101-1
• 作为产物：
  描述：

  (4-methylpent-3-en-1-yl)triphenylphosphonium bromide 在 sodium hexamethyldisilazane 、 silver nitrate 作用下， 以 四氢呋喃 、 乙醇 、 水 为溶剂， 反应 2.5h， 生成 (E)-β-ocimene
  参考文献：
  名称：

  Electronic Tuning of Fischer Carbene Complexes in the Preparation of Bicyclo[3.1.1]heptanones as Taxane A-ring Synthons

  摘要：

  A synthetic route to taxol and other Taxus diterpenes is described which employs as a key step the reaction between a Fischer carbene complex and a 1,6 enyne to construct 1-substituted-7,7-dimethyl-2-methylenebicyclo[3.1.1] heptan-6-ones. It was found that the reaction between complex 2 and 7-methyl-3-methylene-6-octen-1-yne (dienyne 30) yielded a mixture of bicyclo[3.1.1]heptanone 35 and cyclobutenone 36, the latter possibly arising from the migration of the chromium fragment from an electron-rich alkene to a less electron-rich alkene in the vinyl carbene complex intermediate (i.e. 40-42). On this basis, it was expected that bicycloheptanone yields would increase with increasing electron deficiency in the intermediate 40 since this should lead to more competitive CO insertion. This was observed with a series of electronically modified carbene complexes (45 and 48a-d). The more electron deficient complexes gave good yields of bicycloheptanones, thus providing an efficient means for preparing taxane A-ring synthons. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(99)01101-1

文献信息

• Electronic Tuning of Fischer Carbene Complexes in the Preparation of Bicyclo[3.1.1]heptanones as Taxane A-ring Synthons
  作者：Weiqin Jiang、Michael J Fuertes、William D Wulff

  DOI：10.1016/s0040-4020(99)01101-1

  日期：2000.4

  A synthetic route to taxol and other Taxus diterpenes is described which employs as a key step the reaction between a Fischer carbene complex and a 1,6 enyne to construct 1-substituted-7,7-dimethyl-2-methylenebicyclo[3.1.1] heptan-6-ones. It was found that the reaction between complex 2 and 7-methyl-3-methylene-6-octen-1-yne (dienyne 30) yielded a mixture of bicyclo[3.1.1]heptanone 35 and cyclobutenone 36, the latter possibly arising from the migration of the chromium fragment from an electron-rich alkene to a less electron-rich alkene in the vinyl carbene complex intermediate (i.e. 40-42). On this basis, it was expected that bicycloheptanone yields would increase with increasing electron deficiency in the intermediate 40 since this should lead to more competitive CO insertion. This was observed with a series of electronically modified carbene complexes (45 and 48a-d). The more electron deficient complexes gave good yields of bicycloheptanones, thus providing an efficient means for preparing taxane A-ring synthons. (C) 2000 Elsevier Science Ltd. All rights reserved.