(S)-(+)-Methyl (1'-Bromo-1-ferrocenyl)-phenylphosphinite-Borane | 311820-10-7

• 英文名称: (S)-(+)-Methyl (1'-Bromo-1-ferrocenyl)-phenylphosphinite-Borane
• CAS: 311820-10-7
• 化学式: C₂₇H₂₅BBrFeOP
• 分子量: 543.031
• InChiKey: UIHAXPBMRUPZKC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (R)-(-)-Methyl (1-Naphthyl)(4-(trifluoromethyl)phenyl)phosphinite-Borane 、 (S)-(+)-Methyl (1'-Bromo-1-ferrocenyl)-phenylphosphinite-Borane 在 仲丁基锂 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 以70%的产率得到(S,S)-(+)-1-[(1-naphthyl)(4-methoxyphenyl)phosphino]-1'-[(1-naphthyl)((4-trifluoromethyl)phenyl)phosphino]ferrocene
  参考文献：
  名称：

  Phosphorus-Chiral Diphosphines as Ligands in Hydroformylation. An Investigation on the Influence of Electronic Effects in Catalysis

  摘要：

  The phosphorus-chiral diphosphine 1,1'-bis(1-naphthylphenylphosphino)ferrocene (1a) and its new electronically modified derivatives 1b-d bearing methoxy and/or trifluoromethyl groups in para positions of the phenyl rings were investigated as ligands in rhodium-catalyzed (asymmetric) hydroformylation. Depending on ligand basicity, high-pressure NMR and IR characterization of the respective (diphosphine) rhodium dicarbonyl hydride precursor complexes revealed subtle differences in the occupation of bis-equatorial (ee) and equatorial-apical (ea) coordination geometries. The high ee:fa ratio of the four complexes contrasted with the clear ea preference observed for the related achiral compound dppf (1,1'-bis(diphenylphosphino)ferrocene). In the hydroformylation of styrene the best result (50% ee) was obtained by employing the best pi -acceptor ligand 1c, incorporating two p-trifluoromethyl substituents. Substrate electronic variations using 4-methoxystyrene and 4-chlorostyrene showed a pronounced influence on turnover frequencies, branched/linear aldehyde product ratios, and enantiodiscrimination, whereas in the hydroformylation of 1-octene ligand electronic perturbations did affect only the rate, but not the selectivity of the reaction.

  DOI：

  10.1021/om0004489
• 作为产物：
  描述：

  1,1'-dibromoferrocene 、 (R)-(-)-Methyl (1-Naphthyl)(4-methoxyphenyl)phosphinite-Borane 在 仲丁基锂 作用下， 以 四氢呋喃 、 环己烷 为溶剂， 以41%的产率得到(S)-(+)-Methyl (1'-Bromo-1-ferrocenyl)-phenylphosphinite-Borane
  参考文献：
  名称：

  Phosphorus-Chiral Diphosphines as Ligands in Hydroformylation. An Investigation on the Influence of Electronic Effects in Catalysis

  摘要：

  The phosphorus-chiral diphosphine 1,1'-bis(1-naphthylphenylphosphino)ferrocene (1a) and its new electronically modified derivatives 1b-d bearing methoxy and/or trifluoromethyl groups in para positions of the phenyl rings were investigated as ligands in rhodium-catalyzed (asymmetric) hydroformylation. Depending on ligand basicity, high-pressure NMR and IR characterization of the respective (diphosphine) rhodium dicarbonyl hydride precursor complexes revealed subtle differences in the occupation of bis-equatorial (ee) and equatorial-apical (ea) coordination geometries. The high ee:fa ratio of the four complexes contrasted with the clear ea preference observed for the related achiral compound dppf (1,1'-bis(diphenylphosphino)ferrocene). In the hydroformylation of styrene the best result (50% ee) was obtained by employing the best pi -acceptor ligand 1c, incorporating two p-trifluoromethyl substituents. Substrate electronic variations using 4-methoxystyrene and 4-chlorostyrene showed a pronounced influence on turnover frequencies, branched/linear aldehyde product ratios, and enantiodiscrimination, whereas in the hydroformylation of 1-octene ligand electronic perturbations did affect only the rate, but not the selectivity of the reaction.

  DOI：

  10.1021/om0004489