dichloro(η6-p-cymene)[(R)-(2-biphenylyl)(2,2-dimethyl-2-silapropyl)phenylphosphine]ruthenium(II) | 928207-58-3

• 英文名称: dichloro(η6-p-cymene)[(R)-(2-biphenylyl)(2,2-dimethyl-2-silapropyl)phenylphosphine]ruthenium(II)
• 英文别名: [(S)-RuCl2(η6-p-cymene)P(Ph)(2-biphenylyl)CH2SiMe3]
• CAS: 928207-58-3
• 化学式: C₃₂H₃₉Cl₂PRuSi
• 分子量: 654.697
• InChiKey: CQUVARRATXTHTO-DOXBVADSSA-L

反应信息

• 作为产物：
  描述：

  [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂ 、 [(S)-Me3SiCH2P(Ph)(2-biphenylyl)] 以 二氯甲烷 为溶剂， 以90%的产率得到dichloro(η6-p-cymene)[(R)-(2-biphenylyl)(2,2-dimethyl-2-silapropyl)phenylphosphine]ruthenium(II)
  参考文献：
  名称：

  Rhodium or ruthenium units peripherally coordinated to carbosilane dendrimers functionalized with P-stereogenic monophosphines

  摘要：

  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)Si{CH2PPhR(RhCl(COD))} and (CH3)(3)Si{CH2PPhR(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.

  DOI：

  10.1016/j.jorganchem.2006.10.035

文献信息

• Neutral p-cymene ruthenium complexes with P-stereogenic monophosphines. New catalytic precursors in enantioselective transfer hydrogenation and cyclopropanation
  作者：Arnald Grabulosa、Alberto Mannu、Antonio Mezzetti、Guillermo Muller

  DOI：10.1016/j.jorganchem.2011.09.015

  日期：2012.1

  1-phenylethanol. Cationic complexes formed upon treatment of C with one equivalent of AgSbF6 or (Et3O)PF6 are active in the cyclopropanation reaction of styrene and α-methylstyrene by ethyl diazoacetate. Low to moderate conversions (up to 58%), diastereoselectivities (up to 40% de), and moderate enantioselectivities (up to 69% ee) have been found. For both reactions, bulky complexes and C6 in particular

  一家八中性，pseudotetrahedral钢琴凳钌络合物Ç，所述类型的合成将[RuCl 2（p -cymene）（PArPhR）]（Ar为1-萘基，9-菲基和2-联苯基; R = Me中，我-已制备并表征了Pr，OMe，-CH 2 SiMe 3和-CH 2 SiPh 3，包括C6的X射线晶体结构（Ar = 2-联苯基； R =  i -Pr）。这些配合物在叔丁氧基钾存在下催化2-苯丙醇在回流的2-丙醇中催化苯乙酮的不对称氢转移反应，在达到S的24小时后达到完全转化和高达45％ee1-苯基乙醇的对映体。用一当量的AgSbF 6或（Et 3 O）PF 6处理C时形成的阳离子络合物在苯乙烯和α-甲基苯乙烯通过重氮乙酸乙酯的环丙烷化反应中具有活性。已发现低至中等的转化率（高达58％），非对映选择性（高达40％de）和中等对映选择性（高达69％ee）。对于这两种反应，特别是笨重的配合物和C6均能达到最佳效果。