(+)-(1R,2S,5R,6S,8R)-8-isopropenyl-1,5-dimethyl-2-(trimethylsilyl)bicyclo<4.4.0>decan-6-ol | 137895-85-3

• 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: (+)-(1R,2S,5R,6S,8R)-8-isopropenyl-1,5-dimethyl-2-(trimethylsilyl)bicyclo<4.4.0>decan-6-ol
• 英文别名: (1S,4R,4aS,6R,8aR)-4,8a-dimethyl-6-prop-1-en-2-yl-1-trimethylsilyl-1,2,3,4,5,6,7,8-octahydronaphthalen-4a-ol
• CAS: 137895-85-3
• 化学式: C₁₈H₃₄OSi
• 分子量: 294.553
• InChiKey: CGGNXLSZXABNDS-ZBRFXRBCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.24
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (+)-(1R,2S,5R,6S,8R)-8-isopropenyl-1,5-dimethyl-2-(trimethylsilyl)bicyclo<4.4.0>decan-6-ol 在 3,5-二甲基吡唑 、 ferric(III) bromide 、 二氯氧化铬 、 叔丁醇 作用下， 以 二氯甲烷 为溶剂， 反应 38.42h， 生成 solavetivone
  参考文献：
  名称：

  Silicon-promoted ring contractions in the formation of carbocyclic spiro compounds. Total synthesis of (-)-solavetivone

  摘要：

  A new method involving silicon-promoted ring contraction was developed for the synthesis of carbocyclic spiro compounds. In the presence of a Lewis acid, (trimethylsilyl)decalinol 12 and (trimethylsilyl)declain expoide 11 underwent ring contraction in a highly stereoselective manner to afford spiro[4.5]dec-6-enes 14 and 19, respectively. The first total synthesis of optically active solavetivone ((-)-1) was accomplished in 13 steps by use of this new type of reaction as the key step. Utilization of the silicon-promoted ring contraction solves three problems associated with spiro compound synthesis: (1) efficient generation of the quaternary carbon spiro center, (2) full control of the stereoconfiguration of the spiro center during its formation, and (3) stereospecific establishment of chiral centers on both rings of the spiro unit.

  DOI：

  10.1021/jo00029a025
• 作为产物：
  描述：

  7(R)-Isopropenyl-4a(S)-methyl-4,4a,5,6,7,8-hexahydronaphthalen-2(3H)-one 在 三氟化硼乙醚 、 氨 、 甲基锂 、 calcium 、 间氯过氧苯甲酸 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 1,4-二氧六环 、 甲醇 、 乙醚 、 氯仿 为溶剂， 反应 197.47h， 生成 (+)-(1R,2S,5R,6S,8R)-8-isopropenyl-1,5-dimethyl-2-(trimethylsilyl)bicyclo<4.4.0>decan-6-ol
  参考文献：
  名称：

  Silicon-promoted ring contractions in the formation of carbocyclic spiro compounds. Total synthesis of (-)-solavetivone

  摘要：

  A new method involving silicon-promoted ring contraction was developed for the synthesis of carbocyclic spiro compounds. In the presence of a Lewis acid, (trimethylsilyl)decalinol 12 and (trimethylsilyl)declain expoide 11 underwent ring contraction in a highly stereoselective manner to afford spiro[4.5]dec-6-enes 14 and 19, respectively. The first total synthesis of optically active solavetivone ((-)-1) was accomplished in 13 steps by use of this new type of reaction as the key step. Utilization of the silicon-promoted ring contraction solves three problems associated with spiro compound synthesis: (1) efficient generation of the quaternary carbon spiro center, (2) full control of the stereoconfiguration of the spiro center during its formation, and (3) stereospecific establishment of chiral centers on both rings of the spiro unit.

  DOI：

  10.1021/jo00029a025