bis(trisphenylphosphine)(dibenzylideneacetone)palladium(0) | 74576-66-2

• 英文名称: bis(trisphenylphosphine)(dibenzylideneacetone)palladium(0)
• 英文别名: Pd(dibenzylideneacetone)(PPh3)2；Pd⁰(η²-dba)(PPh₃)₂；[Pd(η²-dba)(PPh3)2]；[(η2-dba)Pd(P(C6H5)3)2]；[η2-dba)Pd(P(C6H5)3)2]；Pd(PPh3)2-η2-dba
• CAS: 74576-66-2；153698-17-0
• 化学式: C₅₃H₄₄OP₂Pd
• 分子量: 865.299
• InChiKey: OBBUUUZUERULCK-RRPXAISISA-N

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：

  bis(trisphenylphosphine)(dibenzylideneacetone)palladium(0) 在 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 生成 四(三苯基膦)钯
  参考文献：
  名称：

  Rates and mechanisms of oxidative addition to zerovalent palladium complexes generated in situ from mixtures of Pd0(dba)2 and triphenylphosphine

  摘要：

  The composition of mixtures of Pd0(dba)2 (dba = dibenzylideneacetone) and triphenylphosphine was examined in THF and DMF, as well as their reactivity vis a 'vis oxidative addition of PhI. It is concluded that, at equilibrium, these catalytic systems contain lesser available amounts of the species active in oxidative addition, viz. the low-ligated zerovalent palladium intermediate ''Pd0(PPh3)2'', than Pd0(PPh3)4 solutions do for an identical concentration of zerovalent palladium. This arises because, in contradiction with usual assumptions, dba is a better ligand than triphenylphosphine, for the low-ligated active ''Pd0(PPh3)2'', as evidenced by the small values (0.14) of the equilibrium constants of Pd0(dba)(PPh3)2 + PPh3 + solvent reversible solvent-Pd0(PPh3)3 + dba in THF or DMF. As a result, oxidative addition of PhI to mixtures of Pd0(dba)2 and 2 equiv of triphenylphosphine proceeds at an overall rate that is ca. 10 times less than that to Pd0(PPh3)4. However, it is shown that oxidative addition to the two systems proceeds via the same transient intermediate, the solvated low-ligated ''Pd0(PPh3)2'' moiety, evidencing that coordination by dba is not involved in the transition state of oxidative addition. This validates a posteriori previous assumptions on such transition states made in the literature, particularly for rationalization of enantiomeric selectivity when chiral phosphines are used.

  DOI：

  10.1021/om00032a045
• 作为产物：
  描述：

  bis(dibenzylideneacetone)-palladium⁽⁰⁾ 在 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 生成 bis(trisphenylphosphine)(dibenzylideneacetone)palladium(0)
  参考文献：
  名称：

  Rates and mechanisms of oxidative addition to zerovalent palladium complexes generated in situ from mixtures of Pd0(dba)2 and triphenylphosphine

  摘要：

  The composition of mixtures of Pd0(dba)2 (dba = dibenzylideneacetone) and triphenylphosphine was examined in THF and DMF, as well as their reactivity vis a 'vis oxidative addition of PhI. It is concluded that, at equilibrium, these catalytic systems contain lesser available amounts of the species active in oxidative addition, viz. the low-ligated zerovalent palladium intermediate ''Pd0(PPh3)2'', than Pd0(PPh3)4 solutions do for an identical concentration of zerovalent palladium. This arises because, in contradiction with usual assumptions, dba is a better ligand than triphenylphosphine, for the low-ligated active ''Pd0(PPh3)2'', as evidenced by the small values (0.14) of the equilibrium constants of Pd0(dba)(PPh3)2 + PPh3 + solvent reversible solvent-Pd0(PPh3)3 + dba in THF or DMF. As a result, oxidative addition of PhI to mixtures of Pd0(dba)2 and 2 equiv of triphenylphosphine proceeds at an overall rate that is ca. 10 times less than that to Pd0(PPh3)4. However, it is shown that oxidative addition to the two systems proceeds via the same transient intermediate, the solvated low-ligated ''Pd0(PPh3)2'' moiety, evidencing that coordination by dba is not involved in the transition state of oxidative addition. This validates a posteriori previous assumptions on such transition states made in the literature, particularly for rationalization of enantiomeric selectivity when chiral phosphines are used.

  DOI：

  10.1021/om00032a045
• 作为试剂：
  描述：

  9-溴蒽 、 4-乙烯基苯硼酸 在 bis(trisphenylphosphine)(dibenzylideneacetone)palladium(0) 、 sodium carbonate 作用下， 以 乙醇 、 甲苯 为溶剂， 反应 20.0h， 以95%的产率得到9-(4-vinyl phenyl)anthracene
  参考文献：
  名称：

  Synthesis of new styrylarenes via Suzuki–Miyaura coupling catalysed by highly active, well-defined palladium catalysts

  摘要：

  报告了一种合成具有明确结构的钯(0)配合物[Pd(η²-dba)(PPh3)2](2)、[Pd(η²-dba)(PCy3)2](3)及其晶体结构的有效合成路线。这是首次对含有一个二苯亚甲基丙酮和两个膦配体的钯配合物进行的晶体学表征。描述了一种通过Suzuki-Miyaura偶联反应高效、完全可控地选择性合成单芳基烯烃(5-9)和二苯乙烯烃(10-15)的方法。

  DOI：

  10.1039/c3dt52063c

文献信息

• Regioselectivity in the Sonogashira coupling of 4,6-dichloro-2-pyrone
  作者：Ian J. S. Fairlamb、Ciara T. O'Brien、Zhenyang Lin、King Chung Lam

  DOI：10.1039/b518232h

  日期：——

  The Sonogashira cross-coupling of 4,6-dichloro-2-pyrone with terminal acetylenes proceeds in good yields and high regioselectivity for the 6-position; dibenzylidene acetone (dba) type ligands play a non-innocent role in reactions mediated by Pd(dba)2/PPh3; theoretical studies indicate that C-6 oxidative addition is favoured both kinetically and thermodynamically.

  4,6-二氯-2-吡喃酮与末端炔烃的Sonogashira交叉偶联反应以良好产率和高度区域选择性进行，产物优先在6位生成；二苄叉丙酮（dba）型配体在Pd(dba)2/PPh3催化的反应中发挥着非无辜作用；理论研究表明，C-6的氧化加成在动力学和热力学上都更有利。
• Palladium-Catalyzed Coupling Reactions of Tetrafluoroethylene with Arylzinc Compounds
  作者：Masato Ohashi、Tadashi Kambara、Tsubasa Hatanaka、Hiroki Saijo、Ryohei Doi、Sensuke Ogoshi

  DOI：10.1021/ja109911p

  日期：2011.3.16

  Organofluorine compounds are widely used in all aspects of the chemical industry. Although tetrafluoroethylene (TFE) is an example of an economical bulk organofluorine feedstock, the use of TFE is mostly limited to the production of poly(tetrafluoroethylene) and copolymers with other alkenes. Furthermore, no catalytic transformation of TFE that involves carbon-fluorine bond activation has been reported

  有机氟化合物广泛应用于化学工业的各个方面。尽管四氟乙烯 (TFE) 是经济的散装有机氟原料的一个例子，但 TFE 的使用主要限于生产聚（四氟乙烯）和与其他烯烃的共聚物。此外，迄今为止还没有报道涉及碳-氟键活化的 TFE 催化转化。我们在此报告了在碘化锂存在下，钯催化的 TFE 与芳基锌试剂偶联反应的第一个例子，以优异的产率得到 α,β,β-三氟苯乙烯衍生物。
• Pd-catalysed intramolecular regioselective arylation of 2-pyrones, pyridones, coumarins and quinolones by C–H bond functionalization
  作者：Marie-Therese Nolan、Joshua T.W. Bray、Kevin Eccles、Man Sing Cheung、Zhenyang Lin、Simon E. Lawrence、Adrian C. Whitwood、Ian J.S. Fairlamb、Gerard P. McGlacken

  DOI：10.1016/j.tet.2014.04.029

  日期：2014.10

  The intramolecular arylation of 2-pyrones, 2-pyridones, coumarins and quinolones is reported using Pd-II precatalyst sources without added phosphine ligands. The excellent yields and convenient reagents enables the formation of various analogues containing these moieties, and access to potential biologically active candidates. Stoichiometric studies were carried out to provide an insight into the oxidation addition step. A switch in regioselectivity, together with a hydrodebromination process, was observed in the case of a 3-bromo-2-pyrone. (C) 2014 Elsevier Ltd. All rights reserved.
• Andrieu, Jacques; Braunstein, Pierre; Burrows, Andrew D., Journal of Chemical Research - Part S
  作者：Andrieu, Jacques、Braunstein, Pierre、Burrows, Andrew D.

  DOI：——

  日期：——
• Amatore, Christian; Jutand, Anny; Meyer, Gilbert, Inorganica Chimica Acta, 1998, vol. 273, # 1-2, p. 76 - 84
  作者：Amatore, Christian、Jutand, Anny、Meyer, Gilbert

  DOI：——

  日期：——