α-1-(allyldimethylsilyl)-7-exo-<(benzyloxy)methyl>-β-3,7-dimethyl-α-3,4-epoxybicyclo<4.1.0>heptan-2-one | 143143-75-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: α-1-(allyldimethylsilyl)-7-exo-<(benzyloxy)methyl>-β-3,7-dimethyl-α-3,4-epoxybicyclo<4.1.0>heptan-2-one
• CAS: 143143-75-3
• 化学式: C₂₂H₃₀O₃Si
• 分子量: 370.564
• InChiKey: FZCWSHPYDYIAKD-WQIFRTTPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  26.0
• 可旋转键数：
  7.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  38.83
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  α-1-(allyldimethylsilyl)-7-exo-<(benzyloxy)methyl>-β-3,7-dimethyl-α-3,4-epoxybicyclo<4.1.0>heptan-2-one 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 24.0h， 以77%的产率得到7-exo-<(benzyloxy)methyl>-α-1-(allyldimethylsilyl)-α-3,4-epoxy-β-3,7-dimethyl-β-2-hydroxybicyclo<4.1.0>heptane
  参考文献：
  名称：

  Synthesis of phorbol C-ring analogs: a biomimetic model study on the phorbol to 12-hydroxydaphnetoxin conversion.

  摘要：

  An eight-step synthesis of phorbol C-ring analogs is described. The results of a model study on the phorbol) to 12-hydroxy daphnetoxin biomimetic conversion using a C-9 ester-assisted cyclopropyl carbinyl rearrangement are presented. Under the basic conditions used, the dominant reaction pathway is the ParticiPation Of the C-13 hydroxyl group leading to cleavage of the wrong cyclopropane bond to generate an enone, rather than the desired orthoester. The key step in these synthetic studies is the use of the allyldimethylsilyl functionality as a latent form of hydroxyl group, which facilitates the introduction of the hydroxyl group at cyclic tertiary centers.

  DOI：

  10.1021/jo00046a017
• 作为产物：
  描述：

  carvone diepoxide 在 六甲基磷酰三胺 、 potassium tert-butylate 、 四丁基碘化铵 、 sodium hydride 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 叔丁醇 为溶剂， 反应 22.0h， 生成 α-1-(allyldimethylsilyl)-7-exo-<(benzyloxy)methyl>-β-3,7-dimethyl-α-3,4-epoxybicyclo<4.1.0>heptan-2-one
  参考文献：
  名称：

  Synthesis of phorbol C-ring analogs: a biomimetic model study on the phorbol to 12-hydroxydaphnetoxin conversion.

  摘要：

  An eight-step synthesis of phorbol C-ring analogs is described. The results of a model study on the phorbol) to 12-hydroxy daphnetoxin biomimetic conversion using a C-9 ester-assisted cyclopropyl carbinyl rearrangement are presented. Under the basic conditions used, the dominant reaction pathway is the ParticiPation Of the C-13 hydroxyl group leading to cleavage of the wrong cyclopropane bond to generate an enone, rather than the desired orthoester. The key step in these synthetic studies is the use of the allyldimethylsilyl functionality as a latent form of hydroxyl group, which facilitates the introduction of the hydroxyl group at cyclic tertiary centers.

  DOI：

  10.1021/jo00046a017