(Z)-1,3-bis(phenylseleno)-5,5-bis(ethoxycarbonyl)-2,7-octadien-1-one | 137540-84-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (Z)-1,3-bis(phenylseleno)-5,5-bis(ethoxycarbonyl)-2,7-octadien-1-one
• CAS: 137540-84-2
• 化学式: C₂₆H₂₈O₅Se₂
• 分子量: 578.425
• InChiKey: AGPIBNBTPIXJNC-PYCFMQQDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.54
• 重原子数：
  33.0
• 可旋转键数：
  13.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  69.67
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为产物：
  描述：

  2-烯丙基-2-(2-丙炔基)丙二酸二乙酯 、 一氧化碳 、 二苯基二硒醚 在 bis-triphenylphosphine-palladium(II) chloride 作用下， 以 苯 为溶剂， 110.0 ℃ 、980.59 kPa 条件下， 反应 16.0h， 以60%的产率得到(Z)-1,3-bis(phenylseleno)-5,5-bis(ethoxycarbonyl)-2,7-octadien-1-one
  参考文献：
  名称：

  Palladium-catalyzed addition and carbonylative addition of diaryl disulfides and diselenides to terminal acetylenes

  摘要：

  Novel transition-metal-catalyzed reactions of disulfides and diselenides with acetylenes are described. In the of tetrakis(triphenylphosphine)palladium(0), [Pd(PPh3)4], the (1) of diaryl disulfides and diselenides to terminal acetylenes 1 takes place stereoselectively to give high yields of (Z)-1,2-bis(arylthio)-1-alkenes 2 and (Z)-1,2-bis(arylseleno)-1-alkenes 3, respectively. A mechanistic proposal includes the following: (1) oxidative addition of (ArY)2 [Y = S, Se] to low-valent palladium species, (2) stereoselective cis-thiopalladation or cis-selenopalladation to acetylenes to form a cis-vinylpalladium intermediate, and (3) reductive elimination of the product with retention of the stereochemistry. When the reaction of diaryl disulfides and diselenides with terminal acetylenes is performed under the pressure of carbon monoxide, the carbonylative addition occurs to afford (Z)-1,3-bis(arylthio)-2-alken-1-ones 4 and (Z)-1,3-bis(arylseleno)-2-alken-1-ones 5, respectively. Carbon monoxide is regioselectively incorporated on the side of the terminal carbon of the acetylenes.

  DOI：

  10.1021/ja00026a013