1,1'-bis[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]ferrocene | 214151-82-3

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 1,1'-bis[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]ferrocene
• 英文别名: iron(2+);2,4,8,10-tetratert-butyl-6-cyclopenta-2,4-dien-1-ylbenzo[d][1,3,2]benzodioxaphosphepine
• CAS: 214151-82-3
• 化学式: C₆₆H₈₈FeO₄P₂
• 分子量: 1063.22
• InChiKey: OTYBDIGYSHBHMG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  22.37
• 重原子数：
  73
• 可旋转键数：
  10
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  acetylacetonatodicarbonylrhodium(l) 、 1,1'-bis[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]ferrocene 以 氘代苯 为溶剂， 以53%的产率得到(OC(CH₃)CHC(CH₃)O)Rh(P(OC₆H₂(C(CH₃)3)2)2C₅H₄)2Fe
  参考文献：
  名称：

  Ferrocene Bis(phosphonite)s:  Synthesis and Characterization of a Novel Class of Sterically Congested Ligands¹

  摘要：

  Phosphorus-based ligands continue to play a pivotal role in the development of stereoselective transition-metal-catalyzed reactions. Although phosphine-based ligands have been extensively used in the optimization of catalytic processes, the use of readily modifiable phosphite or phosphonite ligands offers an attractive alternative to phosphine-based ligands. Recently, sterically hindered bis(phosphite) ligands incorporating the seven-membered dibenzo[d,f][1,3,2]dioxaphosphepin ring system were reported to be an effective ligand for rhodium-catalyzed hydroformylation reactions (Figure 1).(2) Van Leeuwen et al. suggested that the large natural bite angle in ligands such as I increases the stereoselectivity of the rhodium (I)-catalyzed hydroformylation reaction.(3) A relationship between the ratio of normal to iso olefin hydroformylation as a function of ligand bite angle has been established.(4) Gladfelter et al. made the important observation that the geometric inclination of the bis (phosphite) ruthenium carbonyl complex (P-Ru-P bond angle of 118.98degrees) prepared from 2 is due to steric rather than electronic factors.(5) Nevertheless, the ratio of iso to normal olefin hydroformylation has been shown in an elegant study by Casey to be subject to electronic effects.(6) In principle, the facile preparation of aryl phosphites or phosphonites with electron-accepting or -donating groups allows for the tailoring of sterically congested bis(phosphonite) ligands based upon the ferrocene motif.

  DOI：

  10.1021/ic010750p
• 作为产物：
  描述：

  二茂铁 、 3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl phosphorochloridite 在 n-butyl lithium 、 N,N,N',N'-tetramethylethylenediamine 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以47.7%的产率得到1,1'-bis[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]ferrocene
  参考文献：
  名称：

  Ferrocene Bis(phosphonite)s:  Synthesis and Characterization of a Novel Class of Sterically Congested Ligands¹

  摘要：

  Phosphorus-based ligands continue to play a pivotal role in the development of stereoselective transition-metal-catalyzed reactions. Although phosphine-based ligands have been extensively used in the optimization of catalytic processes, the use of readily modifiable phosphite or phosphonite ligands offers an attractive alternative to phosphine-based ligands. Recently, sterically hindered bis(phosphite) ligands incorporating the seven-membered dibenzo[d,f][1,3,2]dioxaphosphepin ring system were reported to be an effective ligand for rhodium-catalyzed hydroformylation reactions (Figure 1).(2) Van Leeuwen et al. suggested that the large natural bite angle in ligands such as I increases the stereoselectivity of the rhodium (I)-catalyzed hydroformylation reaction.(3) A relationship between the ratio of normal to iso olefin hydroformylation as a function of ligand bite angle has been established.(4) Gladfelter et al. made the important observation that the geometric inclination of the bis (phosphite) ruthenium carbonyl complex (P-Ru-P bond angle of 118.98degrees) prepared from 2 is due to steric rather than electronic factors.(5) Nevertheless, the ratio of iso to normal olefin hydroformylation has been shown in an elegant study by Casey to be subject to electronic effects.(6) In principle, the facile preparation of aryl phosphites or phosphonites with electron-accepting or -donating groups allows for the tailoring of sterically congested bis(phosphonite) ligands based upon the ferrocene motif.

  DOI：

  10.1021/ic010750p
• 作为试剂：
  描述：

  、 、 衣康酸二甲酯 、 甲醇 、 氢气 在 1,1'-bis[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]ferrocene 铑 作用下， 以 tetrahydrofuran methanol 为溶剂， 反应 90.0h， 以Workup of the reaction mixture gives 492 mg (99% yield) of desired dimethyl 2-methylsuccinate的产率得到甲基丁二酸二甲酯
  参考文献：
  名称：

  Ferrocene bis(phosphonite) ligands and complexes for

  摘要：

  本文描述了新的具有立体阻碍的二(膦酸酯)二茂铁化合物I的合成，相应的过渡金属配合物的合成以及这些配合物在过渡金属催化反应中的应用。

  公开号：

  US05817850A1