benzene;3-diphenylphosphanylpropyl(diphenyl)phosphane;palladium(2+);trifluoromethane

• 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: benzene;3-diphenylphosphanylpropyl(diphenyl)phosphane;palladium(2+);trifluoromethane
• 化学式: C₃₄H₃₁F₃P₂Pd
• 分子量: 664.983
• InChiKey: GJOFTYURFBGZPQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.47
• 重原子数：
  40
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  1,3-双(二苯基膦)丙烷 在 4,4'-二氟联苯 、 1,3-双(二苯基膦)丙烷 作用下， 以 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 24.17h， 生成 benzene;3-diphenylphosphanylpropyl(diphenyl)phosphane;palladium(2+);trifluoromethane
  参考文献：
  名称：

  Nucleophile-Catalyzed, Facile, and Highly Selective C–H Activation of Fluoroform with Pd(II)

  摘要：

  Exceedingly facile (23 degrees C) and chemoselective H-CF3 activation with [(dppp)Pd(Ph)(OH)] in the presence of a Lewis base promoter such as n-Bu3P leads to Pd-CF3 bond formation in nearly quantitative yield. A combined experimental and computational study points to a new mechanism that involves H-bonding Pd-O(H)center dot center dot center dot H-CF3 and nucleophilic attack of the promoter on the metal, followed by a push-pull-type collapse of the resultant five-coordinate Pd(II) intermediate via a polar transition state.

  DOI：

  10.1021/ja409533s

文献信息

• New Vistas in Transmetalation with Discrete “AgCF ₃ ” Species: Implications in Pd‐Mediated Trifluoromethylation Reactions
  作者：Sara Martínez de Salinas、Ángel L. Mudarra、Jordi Benet‐Buchholz、Teodor Parella、Feliu Maseras、Mónica H. Pérez‐Temprano

  DOI：10.1002/chem.201802586

  日期：2018.8.14

  This work describes the employment of discrete “AgCF3” complexes as efficient transmetalating agents to PdII to surmount overlooked challenges related to the transmetalation step in Pd‐catalyzed trifluoromethylation processes. We report the participation of a unique silver ate (Cs)[Ag(CF3)2] complex, under stoichiometric and catalytic conditions, in the unprecedented one‐pot formation of PhCF3 using

  这项工作描述了使用离散的“ AgCF 3 ”配合物作为Pd II的有效重金属化剂，以克服与Pd催化的三氟甲基化过程中的重金属化步骤有关的被忽视的挑战。我们报道了在化学计量和催化条件下，独特的银酸盐（Cs）[Ag（CF 3）2 ]络合物参与了以PhI为起始原料的PhCF 3的空前单锅形成。此外，我们表明，在这些转变中通常忽略的重金属化步骤也可以确定偶联过程的成功或失败。
• Nucleophile-Catalyzed, Facile, and Highly Selective C–H Activation of Fluoroform with Pd(II)
  作者：Shin Takemoto、Vladimir V. Grushin

  DOI：10.1021/ja409533s

  日期：2013.11.13

  Exceedingly facile (23 degrees C) and chemoselective H-CF3 activation with [(dppp)Pd(Ph)(OH)] in the presence of a Lewis base promoter such as n-Bu3P leads to Pd-CF3 bond formation in nearly quantitative yield. A combined experimental and computational study points to a new mechanism that involves H-bonding Pd-O(H)center dot center dot center dot H-CF3 and nucleophilic attack of the promoter on the metal, followed by a push-pull-type collapse of the resultant five-coordinate Pd(II) intermediate via a polar transition state.