2-(diphenylphosphino)-3,4,5,6-tetrafluorobenzaldehyde | 1447768-80-0

• 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: 2-(diphenylphosphino)-3,4,5,6-tetrafluorobenzaldehyde
• 英文别名: 2-(diphenylphosphaneyl)-3,4,5,6-tetrafluorobenzaldehyde
• CAS: 1447768-80-0
• 化学式: C₁₉H₁₁F₄OP
• 分子量: 362.263
• InChiKey: YOISTDNPHMXUHA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.81
• 重原子数：
  25.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  2-(diphenylphosphino)-3,4,5,6-tetrafluorobenzaldehyde 以 四氢呋喃 、 氯仿 为溶剂， 反应 4.0h， 生成 trans-[PdCl₂((E)-3-(2-(diphenylphosphino)-3,4,5,6-tetrafluorophenyl)-1-phenylprop-2-en-1-one)₂]
  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：

  溴五氟苯 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 1.25h， 生成 2-(diphenylphosphino)-3,4,5,6-tetrafluorobenzaldehyde
  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

文献信息

• <i>E</i>–<i>Z</i> Isomerization of Phosphine-Olefin (PEWO-F₄) Ligands Revealed upon PdCl₂ Capture: Facts and Mechanism
  作者：Marconi N. Peñas-Defrutos、Andrea Vélez、Estefanía Gioria、Pablo Espinet

  DOI：10.1021/acs.organomet.9b00679

  日期：2019.12.23

  available) in the X-ray diffraction structures, an E configuration of the double bond. In contrast, the structures of [PdCl2(P-chelate)] display E and Z configurations. The E/Z isomerization of the latter requires first decoordination of the double bond, which then allows for easy rotation about the electron-deficient double bond. Thus, the E/Z equilibria exist for the free and the P-monodentate complexes

  所述PEWO膦- [R 2 P（ø -C 6 ħ 4 CH = CHC（O）PH），R 2 P（ø -C 6 ħ 2 ˚F 2 CH = CHC（O）PH），和R 2 P（ø - ç 6 ˚F 4 CH = CHC（O）PH）和它们的P-单齿络合物反式- [的PdCl 2（P-单齿）2 ]示出了在溶液中和在X射线衍射结构（当可用时），一个è配置双键的。相反，[PdCl 2（P-螯合物）]的结构显示E和Z配置。后者的E / Z异构化需要首先使双键解配位，然后使它容易围绕缺电子的双键旋转。因此，对于游离的和P-单齿的配合物也存在E / Z平衡，但是未观察到，因为它们极易向E异构体位移。它们以[PdCl 2（P-螯合物）]的形式捕获，平衡常数约为K eq≈1-3，可以观察和分离这两种构型。评价它们从顺式-[PdPf 2（THF）2 ]偶联Pf-Pf的能力（Pf = C 6 F5），得到其Δ的值ģ