7,7-Dimethyl-1-ethenyl-2-methylenebicyclo<3.3.1>heptan-6-one | 129966-86-5

• 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: 7,7-Dimethyl-1-ethenyl-2-methylenebicyclo<3.3.1>heptan-6-one
• 英文别名: 1-Ethenyl-7,7-dimethyl-2-methylidenebicyclo[3.1.1]heptan-6-one
• CAS: 129966-86-5
• 化学式: C₁₂H₁₆O
• 分子量: 176.258
• InChiKey: MFRJGANIIOJPSA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  乙烯基-锂 、 7,7-Dimethyl-1-ethenyl-2-methylenebicyclo<3.3.1>heptan-6-one 以 四氢呋喃 为溶剂， 反应 1.0h， 以19%的产率得到(E)-11,11-Dimethyl-8-methylenebicyclo<5.3.1>undec-6-en-2-one
  参考文献：
  名称：

  Synthesis of the bicyclo[5.3.1]undecane moiety (AB ring system) of taxanes

  摘要：

  Intramolecular cycloaddition of unsaturated ketenes 15a, 15b, and 6 give the 1-vinylbicyclo[3.1.1]heptan-6-ones 16a, 16b, and 5 in 51%, 63%, and 30% yield. Addition of vinyllithium to these cyclobutanones at -78-degrees-C gives 1,2-divinylcyclobutane alkoxides that undergo oxy-Cope rearrangements to give (E)-bicyclo[5.3.1]undecenones 20a, 20b, and 27 in 57%, 63%, and 19% yield. These cyclooctenones contain suitable substituents and functionality for elaboration of the AB ring system of taxane diterpenes. The oxy-Cope rearrangement fails if more highly substituted alkenyllithium reagents are used; so this approach cannot be used for introduction of the C ring of taxane diterpenes.

  DOI：

  10.1021/jo00001a060
• 作为产物：
  描述：

  6-甲基-5-庚烯-2-酮 在 4-二甲氨基吡啶 、 乙酸酐 、 铜 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 、 锌 作用下， 以 乙醚 为溶剂， 反应 39.0h， 生成 7,7-Dimethyl-1-ethenyl-2-methylenebicyclo<3.3.1>heptan-6-one
  参考文献：
  名称：

  Synthesis of the bicyclo[5.3.1]undecane moiety (AB ring system) of taxanes

  摘要：

  Intramolecular cycloaddition of unsaturated ketenes 15a, 15b, and 6 give the 1-vinylbicyclo[3.1.1]heptan-6-ones 16a, 16b, and 5 in 51%, 63%, and 30% yield. Addition of vinyllithium to these cyclobutanones at -78-degrees-C gives 1,2-divinylcyclobutane alkoxides that undergo oxy-Cope rearrangements to give (E)-bicyclo[5.3.1]undecenones 20a, 20b, and 27 in 57%, 63%, and 19% yield. These cyclooctenones contain suitable substituents and functionality for elaboration of the AB ring system of taxane diterpenes. The oxy-Cope rearrangement fails if more highly substituted alkenyllithium reagents are used; so this approach cannot be used for introduction of the C ring of taxane diterpenes.

  DOI：

  10.1021/jo00001a060

文献信息

• SNIDER, BARRY B.;ALLENTOFF, ALBAN J., J. ORG. CHEM., 56,(1991) N, C. 321-328
  作者：SNIDER, BARRY B.、ALLENTOFF, ALBAN J.

  DOI：——

  日期：——
• Synthesis of the bicyclo[5.3.1]undecane moiety (AB ring system) of taxanes
  作者：Barry B. Snider、Alban J. Allentoff

  DOI：10.1021/jo00001a060

  日期：1991.1

  Intramolecular cycloaddition of unsaturated ketenes 15a, 15b, and 6 give the 1-vinylbicyclo[3.1.1]heptan-6-ones 16a, 16b, and 5 in 51%, 63%, and 30% yield. Addition of vinyllithium to these cyclobutanones at -78-degrees-C gives 1,2-divinylcyclobutane alkoxides that undergo oxy-Cope rearrangements to give (E)-bicyclo[5.3.1]undecenones 20a, 20b, and 27 in 57%, 63%, and 19% yield. These cyclooctenones contain suitable substituents and functionality for elaboration of the AB ring system of taxane diterpenes. The oxy-Cope rearrangement fails if more highly substituted alkenyllithium reagents are used; so this approach cannot be used for introduction of the C ring of taxane diterpenes.