cis-2,3-bis-(diphenylphosphinomethyl)-norbornene | 1221506-05-3

• 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: cis-2,3-bis-(diphenylphosphinomethyl)-norbornene
• 英文别名: cis-2,3-bis(diphenylphosphinemethyl)norbornene
• CAS: 1221506-05-3
• 化学式: C₃₃H₃₂P₂
• 分子量: 490.565
• InChiKey: DJHWCJQEYVLJCJ-XZYRDJQFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.69
• 重原子数：
  35.0
• 可旋转键数：
  8.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  cis-2,3-bis(tosyloxymethyl)norbornene 、 三苯基膦 在 lithium 作用下， 以 四氢呋喃 为溶剂， 反应 0.33h， 以42%的产率得到cis-2,3-bis-(diphenylphosphinomethyl)-norbornene
  参考文献：
  名称：

  Steric and electronic factors in the promoting activity of diphosphine ligands in cyclohexene hydrocarbomethoxylation catalyzed by palladium acetate

  摘要：

  Cyclohexene hydrocarbomethoxylation catalyzed by Pd(OAc)(2)-p-toluenesulfonic acid-diphosphine systems has been investigated for a wide range of diphosphine structures and concentrations. The factors controlling the activity of the palladium-containing catalysts include the hydrocarbon moiety of the ligand and the mutual arrangement of the phosphine groups. A comparison between the promoting effects of monophosphine and diphosphine ligands has demonstrated that bridged trans-diphosphines are more efficient in kinetic and concentration terms (TOF and P/Pd ratio, respectively). In particular, the promoting activity of diphosphines is one order of magnitude higher than that of triphenylphosphine, and this effect is attained at 8-65 times lower P/Pd ratios. It is discussed how the catalytic properties of the systems depend on the chelate effect and on the geometric compatibility between the diphosphine structure and the arrangement of vacant s and d orbitals of the palladium center.

  DOI：

  10.1134/s0023158412040076

文献信息

• Effect of the structure and concentration of diphosphine ligands on the rate of hydrocarbomethoxylation of cyclohexene catalyzed by palladium acetate/diphosphine/TsOH system
  作者：I.E. Nifant’ev、S.A. Batashev、S.A. Toloraya、A.N. Tavtorkin、N.T. Sevostyanova、A.A. Vorobiev、V.V. Bagrov、V.A. Averyanov

  DOI：10.1016/j.molcata.2011.09.005

  日期：2011.11

  Cyclohexene hydrocarbomethoxylation catalyzed by the Pd(OAc)(2) - p-toluenesulfonic acid - diphosphine systems with broad variation of diphosphine structure and concentration was studied. It was shown that the hydrocarbon part of the structure and the mutual arrangement of the phosphine groups are the factors that control the activity of palladium-containing catalysts. By comparison of the promoting effects of mono and diphosphine ligands, it is demonstrated that bridging trans-diphosphines show higher efficiency with regard to both the kinetic (TOF) and concentration factors (low P/Pd ratios). In particular, their promoting activity is an order of magnitude higher than that for triphenylphosphine at lower P/Pd ratios (8-65 times). The results were interpreted from the standpoint of chelation effect and the geometric matching of the diphosphine structure to the arrangement of vacant s,d-orbitals of the Pd centre. (C) 2011 Elsevier B.V. All rights reserved.