(3aS,4S,6R,7aR)-6-(phenylseleninylmethyl)-4-[(E)-prop-1-enyl]-1,3a,4,6,7,7a-hexahydrofuro[3,4-c]pyran-3-one | 163380-36-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 呋喃吡喃类
• 英文名称: (3aS,4S,6R,7aR)-6-(phenylseleninylmethyl)-4-[(E)-prop-1-enyl]-1,3a,4,6,7,7a-hexahydrofuro[3,4-c]pyran-3-one
• CAS: 163380-36-7
• 化学式: C₁₇H₂₀O₄Se
• 分子量: 367.303
• InChiKey: AGBGPCKTMHYUDO-RIBCMOIVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.84
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (3aS,4S,6R,7aR)-6-(phenylseleninylmethyl)-4-[(E)-prop-1-enyl]-1,3a,4,6,7,7a-hexahydrofuro[3,4-c]pyran-3-one 在 双(三甲基硅烷基)氨基钾 、 对甲苯磺酸 、 二乙胺 、 原甲酸三甲酯 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 42.0h， 生成 (3aR,7S,8R)-3a,6,7,8-Tetrahydro-7-methyl-8-(phenylselenyl)spirofuran-5(3H),2'-<1,3>dioxolan>-1(4H)-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：

  N-(苯硒基)邻苯二甲酰亚胺 在 sodium periodate 、 碳酸氢钠 、 对甲苯磺酸 作用下， 以 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 2.0h， 生成 (3aS,4S,6R,7aR)-6-(phenylseleninylmethyl)-4-[(E)-prop-1-enyl]-1,3a,4,6,7,7a-hexahydrofuro[3,4-c]pyran-3-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.