(1S,3R,4S)-1-ethenyl-3-hydroxy-7,7-dimethylbicyclo[2.2.1]heptan-2-one | 162790-58-1

• 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: (1S,3R,4S)-1-ethenyl-3-hydroxy-7,7-dimethylbicyclo[2.2.1]heptan-2-one
• CAS: 162790-58-1
• 化学式: C₁₁H₁₆O₂
• 分子量: 180.247
• InChiKey: TZVTUUDJXMQREG-XLDPMVHQSA-N

物化性质

• 沸点：
  264.2±33.0 °C(predicted)
• 密度：
  1.180±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1S,3R,4S)-1-ethenyl-3-hydroxy-7,7-dimethylbicyclo[2.2.1]heptan-2-one 在 正丁基锂 、 camphor-10-sulfonic acid 作用下， 以 乙醚 为溶剂， 反应 73.25h， 生成 (1S,2S,3R,4S)-2-Isopropenyl-3-(4-methoxy-benzyloxy)-7,7-dimethyl-1-vinyl-bicyclo[2.2.1]heptan-2-ol
  参考文献：
  名称：

  Bicyclic Systems Related to Taxol. A Direct Means for Implementing C-2 Oxygenation and Demonstration of the Feasibility of α-Ketol Equilibration in a Fully Oxygenated B-Ring Setting

  摘要：

  The feasibility of alpha-ketol equilibration in a fully oxygenated B-ring setting for the rapid, enantioselective construction of an A/B bicyclic model related to Taxol has been examined. The key elements associated with this successful venture include selection of a proper array of protecting groups for the four hydroxyl groups present, suitable catalysis of the 1,2-pinacol-like shift, and an intrinsic dependence on the thermodynamic stabilities of the two alpha-ketol isomers. The key conversion of 13 to 14 is seen to be unidirectional and consequently to offer useful potential serviceability as more advanced thrusts toward Taxol are mounted.

  DOI：

  10.1021/jo971592f
• 作为产物：
  描述：

  [(1S,4R)-1-ethenyl-7,7-dimethyl-2-bicyclo[2.2.1]hept-2-enyl]oxy-trimethylsilane 在 四丁基氟化铵 、 二甲基二环氧乙烷 作用下， 生成 (1S,3R,4S)-1-ethenyl-3-hydroxy-7,7-dimethylbicyclo[2.2.1]heptan-2-one 、 (1S,3S,4S)-3-Hydroxy-7,7-dimethyl-1-vinyl-2-norbornanone
  参考文献：
  名称：

  Stereocontrolled Oxygenation of Camphor Derivatives as a Prelude to the Complete .beta.-Ring Functionalization of Potential Precursors to Taxol and Structural Analogs Thereof

  摘要：

  The possibility of realizing the predominant exo a-hydroxylation of camphor-related ketones is described. Both the direct oxidation of enolate anions with 1-phenyl-N-(phenylsulfonyl)oxaziridine or exposure of the derived silyl enol ethers to dimethyl dioxirane are conducive to exo attack. Following conversion to MOM derivatives, the acidity of the alpha-carbonyl proton is reduced sufficiently to allow direct condensation of these hindered ketones with cyclohexenyllithium reagents. The subsequent anionic oxy-Cope rearrangement of the resulting exo carbinols results in direct conversion to tricyclic products that feature the characteristic C-2,C-9,C-10 B-ring oxygenation pattern resident in taxol. Further, the stereogenic centers are introduced in their proper absolute configuration. The steric demands of the [3,3] sigmatropic shift are discussed and the stereochemical features conducive to the minimization of steric compression subjected to experimental verification.

  DOI：

  10.1021/jo00109a020