7-exo-<(benzyloxy)methyl>-α-1-(allyldimethylsilyl)-β-2,α-4-diacetoxy-α-3,7-dimethylbicyclo<4.1.0>heptane | 139177-19-8

• 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-exo-<(benzyloxy)methyl>-α-1-(allyldimethylsilyl)-β-2,α-4-diacetoxy-α-3,7-dimethylbicyclo<4.1.0>heptane
• CAS: 139177-19-8；143234-68-8
• 化学式: C₂₆H₃₈O₅Si
• 分子量: 458.67
• InChiKey: KQJPELRUNJJVCJ-LARAEHLQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.38
• 重原子数：
  32.0
• 可旋转键数：
  9.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  61.83
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  7-exo-<(benzyloxy)methyl>-α-1-(allyldimethylsilyl)-β-2,α-4-diacetoxy-α-3,7-dimethylbicyclo<4.1.0>heptane 在 溴 、 氟化氢吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以79%的产率得到7-exo-<(benzyloxy)methyl>-α-1-(fluorodimethylsilyl)-β-2,α-4-diacetoxy-α-3,7-dimethylbicyclo<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：

  烯丙基二甲基氯硅烷 在 六甲基磷酰三胺 、 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 三氯化铝 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 41.0h， 生成 7-exo-<(benzyloxy)methyl>-α-1-(allyldimethylsilyl)-β-2,α-4-diacetoxy-α-3,7-dimethylbicyclo<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