(3S,4R)-3-[(1R,2R)-1-hydroxy-2-phenylselanylbutyl]-4-prop-2-enyloxolan-2-one | 163223-25-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (3S,4R)-3-[(1R,2R)-1-hydroxy-2-phenylselanylbutyl]-4-prop-2-enyloxolan-2-one
• CAS: 163223-25-4
• 化学式: C₁₇H₂₂O₃Se
• 分子量: 353.32
• InChiKey: OBMMTKHFNFWLTJ-UKMLZYKCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.94
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3S,4R)-3-[(1R,2R)-1-hydroxy-2-phenylselanylbutyl]-4-prop-2-enyloxolan-2-one 在 sodium periodate 、 碳酸氢钠 、 对甲苯磺酸 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 21.0h， 生成 (3aS,4S,7aR)-1,3a,4,7a-Tetrahydro-6-methyl-4-<(E)-propenyl>-3H-furo<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
• 作为产物：
  描述：

  2-phenylselanylbutanal 、 (R)-4-allyldihydrofuran-2(3H)-one 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以30%的产率得到(3S,4R)-3-[(1R,2R)-1-hydroxy-2-phenylselanylbutyl]-4-prop-2-enyloxolan-2-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.