1,2-bis(4-styryldiphenylphosphino)ethane

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,2-bis(4-styryldiphenylphosphino)ethane
• 英文别名: 2-Bis(4-ethenylphenyl)phosphanylethyl-bis(4-ethenylphenyl)phosphane；2-bis(4-ethenylphenyl)phosphanylethyl-bis(4-ethenylphenyl)phosphane
• 化学式: C₃₄H₃₂P₂
• 分子量: 502.576
• InChiKey: HYKBABPHKVHZKT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9
• 重原子数：
  36
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  4-氯苯乙烯 、 1,2-双(二氯磷基)-乙烷 在 magnesium 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以72%的产率得到1,2-bis(4-styryldiphenylphosphino)ethane
  参考文献：
  名称：

  Effect of Chiral Cavities Associated with Molecularly Imprinted Platinum Centers on the Selectivity of Ligand-Exchange Reactions at Platinum

  摘要：

  The metallomonomer (vinyl dppe)Pt[(R)-Bu2BINOL] (1) was copolymerized with ethylene glycol dimethacrylate to produce the molecularly imprinted polymer (MIP) P1. The chiral imprinting ligand (R)-Bu2BINOL was removed from P1 by treatment with HCl or an excess of alpha,alpha,alpha-trifluoro-m-cresol, BINOL, or Br2BINOL, giving polymers P2-P5. The amount of imprinting ligand released from P1 varied inversely with the steric bulk of the cleaving agent, indicating that a distribution of Pt sites with different accessibilities exists in the MIP. Exposure of P3 (containing Pt(OAr)(2) centers surrounded by (R)-Bu2BINOL-shaped cavities) to rac-BINOL, an imprinting ligand analogue, led to preferential rebinding of the imprinted enantiomer via ligand exchange. Both aggregate selectivity and extent of reaction (percent of the total Pt sites in the MIP that participated in rebinding) increased with rebinding time and with temperature, up to 69% ee and 58% Pt sites rebound, respectively. A positive linear correlation between selectivity and reactivity was observed. Open, easily accessible Pt sites were proposed to be less selective than unreactive sites because their associated chiral cavities are less well-defined and therefore less capable of shape-based enantiodiscrimination. The kinetic selectivity of the least reactive sites in P3 was assessed by sequential rebinding of rac-BINOL and then rac-Br2BINOL. Rebound BINOL was recovered from 8 to 20% of the least reactive Pt sites accessible in the MIP in 89-94% ee. All data indicate that chiral cavities (outer sphere) associated with the reactive Pt centers in these MIPs are responsible for the selectivities observed for stoichiometric ligand-exchange reactions at the metal center.

  DOI：

  10.1021/ja000462c

文献信息

• Highly Efficient Heterogeneous Hydroformylation over Rh-Metalated Porous Organic Polymers: Synergistic Effect of High Ligand Concentration and Flexible Framework
  作者：Qi Sun、Zhifeng Dai、Xiaolong Liu、Na Sheng、Feng Deng、Xiangju Meng、Feng-Shou Xiao

  DOI：10.1021/jacs.5b02122

  日期：2015.4.22

  porous polymers supported with Rh species demonstrate even better catalytic performance in the hydroformylations than the analogue homogeneous catalysts. The sample extraordinary performance could be attributed to the combination of high ligand concentration and flexible framework of the porous polymers. Meanwhile, they can be easily separated and recycled from the reaction systems without losing any

  在溶剂热条件下，通过聚合相应的乙烯基官能化二膦单体，成功合成了一系列具有稳定和柔性骨架的二膦配体构建的多孔聚合物。这些不溶性多孔聚合物可以被多种有机溶剂溶胀，表现出与可溶性类似物相似的行为。这些负载有 Rh 物种的多孔聚合物不仅仅是固定均相催化剂，而且在加氢甲酰化中表现出比类似均相催化剂更好的催化性能。样品非凡的性能可归因于高配体浓度和多孔聚合物柔性骨架的结合。同时，它们可以很容易地从反应系统中分离和回收，而不会失去任何活性和选择性。这种优异的催化性能和易于回收的多相催化剂特性使它们非常有吸引力。这些二膦配体构建的多孔聚合物可能为未来烯烃的加氢甲酰化提供新的平台。