2-(diphenylphosphino)ethyl 3,3',5,5'-tetra-tert-butylbiphenyl-2,2'-diyl phosphite | 878196-44-2

• 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: 2-(diphenylphosphino)ethyl 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)oxyethyl]phosphane
• CAS: 878196-44-2
• 化学式: C₄₂H₅₄O₃P₂
• 分子量: 668.836
• InChiKey: ZEZFEKKTAYFZTC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.9
• 重原子数：
  47
• 可旋转键数：
  10
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.43
• 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：

  二氯甲烷 、 bis(1,5-cyclooctadiene)diiridium(I) dichloride 、 2-(diphenylphosphino)ethyl 3,3',5,5'-tetra-tert-butylbiphenyl-2,2'-diyl phosphite 、 silver tetrafluoroborate 以 乙二醇二甲醚 为溶剂， 以65%的产率得到[Ir(COD)(2-(diphenylphosphino)ethyl 3,3',5,5'-tetra-tert-butylbiphenyl-2,2'-diyl phosphite)]BF4*dichloromethane
  参考文献：
  名称：

  Iridium Complexes with Phosphine−Phosphite Ligands. Structural Aspects and Application in the Catalytic Asymmetric Hydrogenation of N-Aryl Imines

  摘要：

  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.

  DOI：

  10.1021/om050885t