(E)-3-(2-(diphenylphosphino)-3,4,5,6-tetrafluorophenyl)-1-phenylprop-2-en-1-one | 1447768-83-3

• 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: (E)-3-(2-(diphenylphosphino)-3,4,5,6-tetrafluorophenyl)-1-phenylprop-2-en-1-one
• 英文别名: (E)-3-(2-diphenylphosphanyl-3,4,5,6-tetrafluorophenyl)-1-phenylprop-2-en-1-one
• CAS: 1447768-83-3
• 化学式: C₂₇H₁₇F₄OP
• 分子量: 464.399
• InChiKey: ZTJUQBBHDVETMM-WUKNDPDISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  33
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (E)-3-(2-(diphenylphosphino)-3,4,5,6-tetrafluorophenyl)-1-phenylprop-2-en-1-one 以 四氢呋喃 为溶剂， 反应 36.0h， 生成
  参考文献：
  名称：

  氟化活化查尔酮膦RPEWO-F 4的反应性，该活化是由CF活化后与PdCl 2配位引起的

  摘要：

  所述ë膦配体（R = PH，Õ -Tol中，Cy），缩写为RPEWO-F 4，是在溶液中稳定，但他们开发上协调丰富的反应性的PdCl 2。螯合的P-烯烃与PdCl 2的配位最终导致氟化查尔酮基o -C 6 F 4 CH = CHC（O）Ph的Z构象。从那里开始发生涉及C═O基团和F原子活化的环化反应，生成强螯合的PdCl 2（P-卡宾）络合物。络合物中的卡宾碳原子显示出一定的亲电性，这表现为水解，氨解和氧化（具有过氧化物）反应，从而提供了具有新的P，C，O钳，P，C，N钳或PdCl 2的络合物。 P，O-螯合物氟化配体。与[PdCl 2（RPEWO-F 4）]络合物用于Negishi催化剂相比，CF活化反应的催化速率慢。因此，至少在快速重金属化亲核试剂方面，预期此处讨论的反应性不会干扰在Pd催化研究或过程中获得的数据的解释。

  DOI：

  10.1021/acs.organomet.0c00019
• 作为产物：
  描述：

  (2-bromo-3,4,5,6-tetrafluorophenyl)diphenylphosphine 在 正丁基锂 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 3.25h， 生成 (E)-3-(2-(diphenylphosphino)-3,4,5,6-tetrafluorophenyl)-1-phenylprop-2-en-1-one
  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
• 作为试剂：
  描述：

  2-碘苯甲酸乙酯, 、 diethylzinc 在 双(乙腈)氯化钯(II) 、 (E)-3-(2-(diphenylphosphino)-3,4,5,6-tetrafluorophenyl)-1-phenylprop-2-en-1-one 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.0h， 以72%的产率得到邻乙基苯甲酸乙酯
  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

• Understanding the Use of Phosphine-(EWO) Ligands in Negishi Cross-Coupling: Experimental and Density Functional Theory Mechanistic Study
  作者：Estefanía Gioria、Juan del Pozo、Agustí Lledós、Pablo Espinet

  DOI：10.1021/acs.organomet.1c00001

  日期：2021.7.26

  2-(trans-CH═CHCOPh)–C6F4 (PhPEWO-F) and other PEWO ligands are well-known promoters of C–C reductive eliminations and very effective in Negishi couplings. As an example, the efficient Negishi coupling of (C6F5)–I and Zn(C6F5)2 is reported. The thorough experimental study of the steps involved in the catalytic cycle uncovers the potential weakness of this ligand that could frustrate at some points the desired

  易于制备的半稳定性配体 1-(PPh 2 ),2-( trans -CH=CHCOPh)–C 6 F 4 (PhPEWO-F) 和其他 PEWO 配体是众所周知的 C–C 还原消除促进剂，并且非常有效根岸联轴器。例如，(C 6 F 5 )–I 和 Zn(C 6 F 5 ) 2的有效 Negishi 耦合被报道。对催化循环中涉及的步骤的彻底实验研究揭示了这种配体的潜在弱点，它可能会在某些时候阻碍所需的循环，并提供一些简单的预防措施来保持催化循环有效工作。密度泛函理论 (DFT) 计算完成了实验研究，并提供了对不可观察的过渡态和中间体的洞察，比较了还原消除和烯烃插入之间的潜在冲突。我们的结果展示了由吸电子配体的强反式效应促进的金属转移步骤的重要性，以及有机锌亲核试剂的选择，这对于确保快速基团交换和催化反应的积极结果至关重要。