2-(diphenylphosphino)phenyl 3,3',5,5'-tetra-tert-butylbiphenyl-2,2'-diyl phosphite | 878196-43-1

• 英文名称: 2-(diphenylphosphino)phenyl 3,3',5,5'-tetra-tert-butylbiphenyl-2,2'-diyl phosphite
• 英文别名: Diphenyl-[2-(2,4,8,10-tetratert-butylbenzo[d][1,3,2]benzodioxaphosphepin-6-yl)oxyphenyl]phosphane
• CAS: 878196-43-1
• 化学式: C₄₆H₅₄O₃P₂
• 分子量: 716.88
• InChiKey: BNTSWRKVRFFKEK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14.6
• 重原子数：
  51
• 可旋转键数：
  9
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  [bis(2-methylallyl)cycloocta-1,5-diene]ruthenium(II) 、 2-(diphenylphosphino)phenyl 3,3',5,5'-tetra-tert-butylbiphenyl-2,2'-diyl phosphite 以 正己烷 为溶剂， 以82%的产率得到
  参考文献：
  名称：

  Synthesis, Characterization, and Reactivity of Ruthenium Bis-Allyl Complexes with Chiral Phosphine-Phosphite Ligands

  摘要：

  A series of ruthenium bis-allyl complexes of formula Ru(eta(3)-2-MeC3H4)(2)(P-OP) (I) which incorporate chiral phosphine-phosphite ligands (P-OP) have been prepared and characterized. Compounds I exist in solution as a mixture of two diastereomers (maj and min) differing in the configuration at the metal. Both isomers are in equilibrium in solution, and their ratio varies with the nature of the P-OP ligand. Along the series, higher values of the maj/min ratio were observed with complexes bearing less sterically encumbered phosphite groups. In reactions of compounds I with protic reagents removal of one or two ally! ligands has been observed. Thus, reaction of 1h with pentachlorophenol produces the mixed allyl-phenoxide 3h, whereas reaction of la or 1h with tiglic acid produces the corresponding tiglates 4a,h, respectively. In addition, compounds I generate active catalysts for the hydrogenation of tiglic and 2-methyl-2-pentenoic acids. By appropriate optimization of the structure of the P-OP ligand, enantioselectivities up to 89% ee were obtained in these reactions. In addition, complexes I also catalyze the ROMP reaction of norbornene, although low initiation rates have been observed for this process.

  DOI：

  10.1021/om300018s

文献信息

• Iridium Complexes with Phosphine−Phosphite Ligands. Structural Aspects and Application in the Catalytic Asymmetric Hydrogenation of N-Aryl Imines
  作者：Sergio Vargas、Miguel Rubio、Andrés Suárez、Diego del Río、Eleuterio Álvarez、Antonio Pizzano

  DOI：10.1021/om050885t

  日期：2006.2.1

  A family of modularly designed phosphine-phosphites (P-OP), possessing a C-C-O backbone, has been synthesized and evaluated in the iridium-catalyzed asymmetric hydrogenation of N-aryl imines. The enantioselectivity of this reaction is highly dependent on the nature of the ligand, and catalysts bridged by an oxyethylene fragment have produced significantly higher enantiomeric excesses (Delta ee > 20%) than their o-oxyphenylene counterparts. Structural studies by X-ray crystallography and NMR spectroscopy of complexes with the formulation [Ir(COD)(P-OP)]BF4 and Ir(Cl)(CO)(P-OP), complemented by DFT calculations of model compounds of the chlorocarbonyls, have shown important differences between complexes bridged by an aliphatic or an aromatic bridge, regarding the iridacycle conformation and the location of phosphine substiments. Catalyst optimization has afforded enantioselectivities from 72 to 85% ee in the hydrogenation of several N-aryl imines.