[PdCl2((Z)-diphenyl(2,3,4,5-tetrafluoro-6-(prop-1-enyl)-phenyl)phosphine)] | 1447768-86-6

• 英文名称: [PdCl2((Z)-diphenyl(2,3,4,5-tetrafluoro-6-(prop-1-enyl)-phenyl)phosphine)]
• 英文别名: [PdCl₂((Z)-diphenyl(2,3,4,5-tetrafluoro-6-(prop-1-enyl)-phenyl)phosphine)]
• CAS: 1447768-86-6
• 化学式: C₂₁H₁₅Cl₂F₄PPd
• 分子量: 551.643
• InChiKey: YICFAGYALZARET-XTZGJZTASA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [PdCl2((Z)-diphenyl(2,3,4,5-tetrafluoro-6-(prop-1-enyl)-phenyl)phosphine)] 在 三苯基膦 作用下， 生成 (Z)-diphenyl(2,3,4,5-tetrafluoro-6-(prop-1-enyl)-phenyl)phosphine 、 (E)-diphenyl(2,3,4,5-tetrafluoro-6-(prop-1-enyl)-phenyl)phosphine
  参考文献：
  名称：

  Phosphines with Tethered Electron-Withdrawing Olefins as Ligands for Efficient Pd-Catalyzed Aryl-Alkyl Coupling

  摘要：

  A group of phosphine/alkene ligands L = Ph2P(2-RC6F4) (R = CH=CHMe, CH=CHPh, CH=CHCOPh) or Ph2P(CH2)(2)CF=CF2 and their [PdCl2L] complexes have been prepared. These phosphines are easy to prepare and fairly stable toward oxidation. Their palladium complexes feature chelated L structures with the double bond coordinated as the Z isomer, except for Ph2P(CH2)(2)CF=CF2, where the double bond is not coordinated and the complex is a dimer with Cl bridges. The ligands have been tested for their activity in the Negishi palladium-catalyzed aryl-alkyl coupling, where there is a competition of coupling and reduction products. Only the ligands forming chelated Pd-II complexes rise the coupling/reduction ratio to values 42/58 or higher. Of these, it is the ligand bearing the more electron-withdrawing substituent (R = CH=CHCOPh) that is the one producing remarkably high selectivity toward coupling: 90/10 under the usual Negishi conditions, and noticeably higher (97/3) if the proportion of ZnEt2 in the reaction is lowered. These results fit well with the hypothesis that chelating phosphines with tethered electron-acceptor olefins improve the selectivity toward coupling products mostly because they reduce the activation barrier for C C coupling, and not because they protect the complex from beta-H elimination.

  DOI：

  10.1021/om4004303
• 作为产物：
  描述：

  双(乙腈)氯化钯(II) 、 (E)-diphenyl(2,3,4,5-tetrafluoro-6-(prop-1-enyl)-phenyl)phosphine 以 四氢呋喃 为溶剂， 反应 5.0h， 以76%的产率得到[PdCl2((Z)-diphenyl(2,3,4,5-tetrafluoro-6-(prop-1-enyl)-phenyl)phosphine)]
  参考文献：
  名称：

  Phosphines with Tethered Electron-Withdrawing Olefins as Ligands for Efficient Pd-Catalyzed Aryl-Alkyl Coupling

  摘要：

  A group of phosphine/alkene ligands L = Ph2P(2-RC6F4) (R = CH=CHMe, CH=CHPh, CH=CHCOPh) or Ph2P(CH2)(2)CF=CF2 and their [PdCl2L] complexes have been prepared. These phosphines are easy to prepare and fairly stable toward oxidation. Their palladium complexes feature chelated L structures with the double bond coordinated as the Z isomer, except for Ph2P(CH2)(2)CF=CF2, where the double bond is not coordinated and the complex is a dimer with Cl bridges. The ligands have been tested for their activity in the Negishi palladium-catalyzed aryl-alkyl coupling, where there is a competition of coupling and reduction products. Only the ligands forming chelated Pd-II complexes rise the coupling/reduction ratio to values 42/58 or higher. Of these, it is the ligand bearing the more electron-withdrawing substituent (R = CH=CHCOPh) that is the one producing remarkably high selectivity toward coupling: 90/10 under the usual Negishi conditions, and noticeably higher (97/3) if the proportion of ZnEt2 in the reaction is lowered. These results fit well with the hypothesis that chelating phosphines with tethered electron-acceptor olefins improve the selectivity toward coupling products mostly because they reduce the activation barrier for C C coupling, and not because they protect the complex from beta-H elimination.

  DOI：

  10.1021/om4004303