(1'S,2'S,4'S,5'R,9'S)-5'-methyl-1'-phenylselanylspiro[1,3-dioxolane-2,7'-11-oxatricyclo[7.3.0.02,4]dodecane]-12'-one | 163380-44-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1'S,2'S,4'S,5'R,9'S)-5'-methyl-1'-phenylselanylspiro[1,3-dioxolane-2,7'-11-oxatricyclo[7.3.0.02,4]dodecane]-12'-one
• CAS: 163380-44-7
• 化学式: C₂₀H₂₄O₄Se
• 分子量: 407.368
• InChiKey: HLXPFYVPRPDXPQ-RREVIBGHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.16
• 重原子数：
  25
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1'S,2'S,4'S,5'R,9'S)-5'-methyl-1'-phenylselanylspiro[1,3-dioxolane-2,7'-11-oxatricyclo[7.3.0.02,4]dodecane]-12'-one 在 双(三甲基硅烷基)氨基钾 作用下， 以 乙二醇二甲醚 、 甲苯 为溶剂， 反应 2.0h， 以76%的产率得到(1'S,2'S,4'S,5'R,9'R)-5'-methylspiro[1,3-dioxolane-2,7'-11-oxatricyclo[7.3.0.02,4]dodecane]-12'-one
  参考文献：
  名称：

  Suitability of the Claisen ring expansion protocol for crenulide diterpene construction

  摘要：

  An enantiospecific synthesis of optically pure 2 a molecule possessing the ring system characteristic of the crenulide diterpenes, is reported. The nine-step sequence began with the previously described R lactone 6. The early bond-forming reactions include an aldol condensation with crotonaldehyde and intramolecular selenonium ion-promoted cyclization with participation by the neighboring hydroxyl group. Selenoxide elimination made possible the acquisition of allyl vinyl ether 4. Thermal activation of the latter in hot mesitylene proceeded via a Claisen ring expansion pathway to give 36a. This key intermediate was then ketalized, subjected to Simmons-Smith cyclopropanation, and carried through a selenoxide elimination step to arrive ultimately at 2. Selected transformations of the medium-ring bicyclic lactones are described, accompanied by X-ray crystallographic studies to substantiate the stereochemical assignments advanced throughout the investigation.

  DOI：

  10.1021/jo00110a053
• 作为产物：
  描述：

  (R)-4-allyldihydrofuran-2(3H)-one 在 六甲基磷酰三胺 、 sodium periodate 、 diethylzinc 、 双(三甲基硅烷基)氨基钾 、 碳酸氢钠 、 对甲苯磺酸 、 二乙胺 、 lithium diisopropyl amide 、 原甲酸三甲酯 作用下， 以 四氢呋喃 、 甲醇 、 乙二醇二甲醚 、 正己烷 、 二氯甲烷 、 水 、 甲苯 、 均三甲苯 、 苯 为溶剂， 反应 26.08h， 生成 (1'S,2'S,4'S,5'R,9'S)-5'-methyl-1'-phenylselanylspiro[1,3-dioxolane-2,7'-11-oxatricyclo[7.3.0.02,4]dodecane]-12'-one
  参考文献：
  名称：

  Suitability of the Claisen ring expansion protocol for crenulide diterpene construction

  摘要：

  An enantiospecific synthesis of optically pure 2 a molecule possessing the ring system characteristic of the crenulide diterpenes, is reported. The nine-step sequence began with the previously described R lactone 6. The early bond-forming reactions include an aldol condensation with crotonaldehyde and intramolecular selenonium ion-promoted cyclization with participation by the neighboring hydroxyl group. Selenoxide elimination made possible the acquisition of allyl vinyl ether 4. Thermal activation of the latter in hot mesitylene proceeded via a Claisen ring expansion pathway to give 36a. This key intermediate was then ketalized, subjected to Simmons-Smith cyclopropanation, and carried through a selenoxide elimination step to arrive ultimately at 2. Selected transformations of the medium-ring bicyclic lactones are described, accompanied by X-ray crystallographic studies to substantiate the stereochemical assignments advanced throughout the investigation.

  DOI：

  10.1021/jo00110a053

文献信息

• Suitability of the Claisen ring expansion protocol for crenulide diterpene construction
  作者：Leo A. Paquette、Jesus Ezquerra、Wei He

  DOI：10.1021/jo00110a053

  日期：1995.3

  An enantiospecific synthesis of optically pure 2 a molecule possessing the ring system characteristic of the crenulide diterpenes, is reported. The nine-step sequence began with the previously described R lactone 6. The early bond-forming reactions include an aldol condensation with crotonaldehyde and intramolecular selenonium ion-promoted cyclization with participation by the neighboring hydroxyl group. Selenoxide elimination made possible the acquisition of allyl vinyl ether 4. Thermal activation of the latter in hot mesitylene proceeded via a Claisen ring expansion pathway to give 36a. This key intermediate was then ketalized, subjected to Simmons-Smith cyclopropanation, and carried through a selenoxide elimination step to arrive ultimately at 2. Selected transformations of the medium-ring bicyclic lactones are described, accompanied by X-ray crystallographic studies to substantiate the stereochemical assignments advanced throughout the investigation.