(1S,3R,4S)-3-(4-Methoxy-benzyloxy)-7,7-dimethyl-1-vinyl-bicyclo[2.2.1]heptan-2-one | 200704-86-5

• 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: (1S,3R,4S)-3-(4-Methoxy-benzyloxy)-7,7-dimethyl-1-vinyl-bicyclo[2.2.1]heptan-2-one
• 英文别名: (1S,3R,4S)-1-ethenyl-3-[(4-methoxyphenyl)methoxy]-7,7-dimethylbicyclo[2.2.1]heptan-2-one
• CAS: 200704-86-5
• 化学式: C₁₉H₂₄O₃
• 分子量: 300.398
• InChiKey: RCNWQYVMKXISOH-MDZRGWNJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1S,3R,4S)-3-(4-Methoxy-benzyloxy)-7,7-dimethyl-1-vinyl-bicyclo[2.2.1]heptan-2-one 、 tert-butyl-[(Z)-6-iodo-4-methylidenehex-5-enoxy]-dimethylsilane 在 叔丁基锂 作用下， 以 乙醚 、 正戊烷 为溶剂， 反应 3.53h， 以96%的产率得到(1S,2S,3R,4S)-2-[(Z)-6-[tert-butyl(dimethyl)silyl]oxy-3-methylidenehex-1-enyl]-1-ethenyl-3-[(4-methoxyphenyl)methoxy]-7,7-dimethylbicyclo[2.2.1]heptan-2-ol
  参考文献：
  名称：

  9,10环乙缩醛立体化学对高度功能化的紫杉醇（Taxol）前体中α-酮醇重排的可行操作的影响。

  摘要：

  报道了对映体纯的立体异构体9,10-环缩醛的收敛，立体控制合成，其设计作用是作为紫杉醇的潜在前体。这些高级中间体经过多重功能化处理，并带有桥头α-酮醇阵列，这对于将异构化成适当的骨架至关重要。与通过MM3计算获得的相对应变能值一致，在这两个族之间观察到了二分法。虽然转熔缩醛未能发生桥迁移，但其顺式对应物却如此有效。实际上，异构化反应非常快，现在可以排除在C2处的氧化。还详细说明了几种不寻常的跨环氢化物转移的操作。

  DOI：

  10.1021/jo020627v
• 作为产物：
  描述：

  2,2,2-三氯代亚氨逐乙酸-4-甲氧基苄酯 、 (1S,3R,4S)-1-ethenyl-3-hydroxy-7,7-dimethylbicyclo[2.2.1]heptan-2-one 在 camphor-10-sulfonic acid 作用下， 以 乙醚 为溶剂， 反应 72.0h， 以89%的产率得到(1S,3R,4S)-3-(4-Methoxy-benzyloxy)-7,7-dimethyl-1-vinyl-bicyclo[2.2.1]heptan-2-one
  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

文献信息

• Effect of 9,10-Cyclic Acetal Stereochemistry on Feasible Operation of the α-Ketol Rearrangement in Highly Functionalized Paclitaxel (Taxol) Precursors
  作者：Leo A. Paquette、John E. Hofferberth

  DOI：10.1021/jo020627v

  日期：2003.3.1

  The convergent, stereocontrolled synthesis of enantiopure stereoisomeric 9,10-cyclic acetals, whose designed role was to serve as potential precursors to Taxol, is reported. These advanced intermediates are multiply functionalized and carry a bridgehead alpha-ketol array which was key to isomerization into the proper framework. In agreement with relative strain energy values obtained by MM3 calculations

  报道了对映体纯的立体异构体9,10-环缩醛的收敛，立体控制合成，其设计作用是作为紫杉醇的潜在前体。这些高级中间体经过多重功能化处理，并带有桥头α-酮醇阵列，这对于将异构化成适当的骨架至关重要。与通过MM3计算获得的相对应变能值一致，在这两个族之间观察到了二分法。虽然转熔缩醛未能发生桥迁移，但其顺式对应物却如此有效。实际上，异构化反应非常快，现在可以排除在C2处的氧化。还详细说明了几种不寻常的跨环氢化物转移的操作。
• 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
  作者：Qingbei Zeng、Simon Bailey、Ting-Zhong Wang、Leo A. Paquette

  DOI：10.1021/jo971592f

  日期：1998.1.1

  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.