diethyl 2-allyl-2-(hex-5-en-2-ynyl)malonate | 1253512-39-8

• 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: diethyl 2-allyl-2-(hex-5-en-2-ynyl)malonate
• CAS: 1253512-39-8
• 化学式: C₁₆H₂₂O₄
• 分子量: 278.348
• InChiKey: DCDSEBJUEXQQLS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.64
• 重原子数：
  20.0
• 可旋转键数：
  8.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  一氧化碳 、 diethyl 2-allyl-2-(hex-5-en-2-ynyl)malonate 在 di(rhodium)tetracarbonyl dichloride 、 (S)-DTBM-MeOBIPHEP 、 silver trifluoromethanesulfonate 作用下， 以 四氢呋喃 为溶剂， 反应 7.0h， 以62%的产率得到diethyl 6-allyl-5-oxo-3,3a,4,5-tetrahydropentalene-2,2(1H)-dicarboxylate
  参考文献：
  名称：

  2,2′‐Bis[bis(3,5‐di‐tert‐butyl‐4‐methoxyphenyl)phosphino]‐6,6′‐dimethoxy‐1,1′‐biphenyl in Intramolecular Rhodium(I)‐Catalyzed Asymmetric Pauson–Khand‐Type Reactions

  摘要：

  AbstractA cationic rhodium(I)/2,2′‐bis[bis(3,5‐di‐tert‐butyl‐4‐methoxyphenyl)phosphino]‐6,6′‐dimethoxy‐1,1′‐biphenyl (DTBM‐MeO‐BIPHEP) catalyst was highly efficient for the asymmetric catalytic Pauson–Khand reaction, especially for those substrates containing aryl group‐substituted alkynes. The formation of the products that were derived from a β‐hydride eliminated intermediate 5 was completely suppressed over a wide range of substrates. This reaction was a serious process competing reaction with the migratory CO insertion that led to the Pauson–Khand reaction product and often substantially ruined the chemical yield of the Pauson–Khand reaction. The advantages of this system were clearly demonstrated for previously troublesome substrates, N‐tosyl‐ (1b) and malonate‐tethered 1,6‐enynes (1c), that exhibited a higher enantioselectivity without a loss in the chemical yields. The obvious beneficial effects were attributed to the synergic effect of various factors, such as the electron density of the phosphorus of the ligand, the dihedral angles of the atropisomeric ligand, and the substitution on the phosphine aryl rings which play a crucial role in the stereochemical outcome of Rh‐catalyzed Pauson–Khand reaction.

  DOI：

  10.1002/adsc.201000221
• 作为产物：
  描述：

  2-烯丙基-2-(2-丙炔基)丙二酸二乙酯 、 3-溴丙烯 在 copper(l) iodide 、 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 6.0h， 以98%的产率得到diethyl 2-allyl-2-(hex-5-en-2-ynyl)malonate
  参考文献：
  名称：

  2,2′‐Bis[bis(3,5‐di‐tert‐butyl‐4‐methoxyphenyl)phosphino]‐6,6′‐dimethoxy‐1,1′‐biphenyl in Intramolecular Rhodium(I)‐Catalyzed Asymmetric Pauson–Khand‐Type Reactions

  摘要：

  AbstractA cationic rhodium(I)/2,2′‐bis[bis(3,5‐di‐tert‐butyl‐4‐methoxyphenyl)phosphino]‐6,6′‐dimethoxy‐1,1′‐biphenyl (DTBM‐MeO‐BIPHEP) catalyst was highly efficient for the asymmetric catalytic Pauson–Khand reaction, especially for those substrates containing aryl group‐substituted alkynes. The formation of the products that were derived from a β‐hydride eliminated intermediate 5 was completely suppressed over a wide range of substrates. This reaction was a serious process competing reaction with the migratory CO insertion that led to the Pauson–Khand reaction product and often substantially ruined the chemical yield of the Pauson–Khand reaction. The advantages of this system were clearly demonstrated for previously troublesome substrates, N‐tosyl‐ (1b) and malonate‐tethered 1,6‐enynes (1c), that exhibited a higher enantioselectivity without a loss in the chemical yields. The obvious beneficial effects were attributed to the synergic effect of various factors, such as the electron density of the phosphorus of the ligand, the dihedral angles of the atropisomeric ligand, and the substitution on the phosphine aryl rings which play a crucial role in the stereochemical outcome of Rh‐catalyzed Pauson–Khand reaction.

  DOI：

  10.1002/adsc.201000221