[(S)-Si(CH2CH2SiMe2CH2P(Ph)(9-phenanthryl)] | 882050-79-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: [(S)-Si(CH2CH2SiMe2CH2P(Ph)(9-phenanthryl)]
• 英文别名: (S)-[dimethyl-[2-[tris[2-[dimethyl-[[phenanthren-9-yl(phenyl)phosphanyl]methyl]silyl]ethyl]silyl]ethyl]silyl]methyl-phenanthren-9-yl-phenylphosphane
• CAS: 882050-79-5
• 化学式: C₁₀₀H₁₀₄P₄Si₅
• 分子量: 1570.25
• InChiKey: NMIQYDWXSBENSZ-PQPKIRSBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  26.18
• 重原子数：
  109
• 可旋转键数：
  28
• 环数：
  16.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (2-methylallyl)palladium-chloride dimer 、 [(S)-Si(CH2CH2SiMe2CH2P(Ph)(9-phenanthryl)] 以 二氯甲烷 为溶剂， 以98%的产率得到
  参考文献：
  名称：

  碳硅烷树状聚合物被P-Stereogenic Monophosphines外围功能化。对苯乙烯的不对称Hydrovinylation他们配合烯丙基钯催化性能†

  摘要：

  通过将受保护的BH 3 -LiCH 2 PPhR（R = 2-联苯基，9-菲基）与第0代和第一代氯碳硅烷树状大分子反应，然后用吗啉和随后进行色谱纯化。由于树枝状聚合物所有臂的功能不完全，因此无法获得带有9-菲基取代的膦的第一代树枝状聚合物。与双核烯丙基络合物[钯（μ-Cl）的（η手性树枝状聚合物的反应3 -2-MEC 3 ħ 4）] 2使我们能够接枝的PdCl（η 3 -2-MEC 3 ħ 4）单位。这些物质的完整表征是通过多核NMR光谱（包括2D实验），质谱法和旋光度测定来实现的。在苯乙烯的不对称加氢乙烯基化反应中测试了新的palladodendrimers的催化性能。为了评估可能的树突作用，制备了两种模型手性化合物（CH 3）3 SiCH 2 PPhR。在活性，选择性和对映体过量方面的结果在很大程度上取决于膦和卤化物抽象剂的性质。使用含有2-联苯基取代的膦和NaBARF（79％ee的S

  DOI：

  10.1021/om050915s

文献信息

• Rhodium or ruthenium units peripherally coordinated to carbosilane dendrimers functionalized with P-stereogenic monophosphines
  作者：Lara-Isabel Rodríguez、Oriol Rossell、Miquel Seco、Guillermo Muller

  DOI：10.1016/j.jorganchem.2006.10.035

  日期：2007.1

  Carbosilane dendrimers containing P-stereogenic monophosphines as terminal groups, Dend-CH2PPhR)(n)(R = 2-biphenylyl or 9-phenanthryt), were reacted with [RhCl(COD)](2) or [RUCl2(p-cymene)](2) to afford the corresponding chiral metalladendrimers Dend-CH2PPhR(RhCl(COD))}(n) or Dend-CH2PPhR(RuCl2(p-cymene))}(n), respectively. Attempts to obtain the first generation Ru-clendrimer for R = 2-biphenylyl proved unsuccessful, probably due to the steric hindrance of R. Complete characterization of these species was achieved by multinuclear NMR spectra, including 2D experiments, mass spectrometry, and optical rotation determinations. The catalytic properties of the rhodium dendrimers were tested in the hydrogenation of dimethylitaconate and those of the ruthenium derivatives in the asymmetric hydrogen transfer of acetophenone. The following model chiral compounds, (CH3)(3)SiCH2PPhR(RhCl(COD))} and (CH3)(3)SiCH2PPhR(RuCl2(p-cymene))}, were prepared in order to detect potential dendritic effects. All compounds were active in the catalytic conditions tested, but low or null e.e. were found. (c) 2006 Elsevier B.V. All rights reserved.