(+/-)-2-[2-(diphenylphosphino)phenyl]-5,6-dihydro-4-phenyl-4H-1,3-oxazine | 292140-03-5

• 英文名称: (+/-)-2-[2-(diphenylphosphino)phenyl]-5,6-dihydro-4-phenyl-4H-1,3-oxazine
• 英文别名: diphenyl-[2-(4-phenyl-5,6-dihydro-4H-1,3-oxazin-2-yl)phenyl]phosphane
• CAS: 292140-03-5
• 化学式: C₂₈H₂₄NOP
• 分子量: 421.478
• InChiKey: OALVLWFVLAGLGA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.35
• 重原子数：
  31.0
• 可旋转键数：
  5.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  21.59
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  ammonium hexafluorophosphate 、 di-μ-chlorobis[(η(3)-1,3-dimethylallyl)palladium(II)] 、 (+/-)-2-[2-(diphenylphosphino)phenyl]-5,6-dihydro-4-phenyl-4H-1,3-oxazine 以 乙醇 为溶剂， 生成 (+/-)-[2-[2-(diphenylphosphino-χP)phenyl]-5,6-dihydro-4-phenyl-4H-1,3-oxazine-χN](η3-methylbut-2-enyl)palladium(II) hexafluorophosphate
  参考文献：
  名称：

  摘要：

  The novel chiral P,N-ligand 2-[2-(diphenylphosphino)phenyl]-5,6-dihydro-4-phenyl-4H-1,3-oxazine (4) was synthesized. The corresponding {dihydro[(phosphino-xP)aryl]oxazine-xN} (eta(3)-diphenylallyl)palladium(II) hexafluorophosphate 5 and the analogous [Pd(eta(3)-1,3-dimethylallyl)] complex 6 were investigated by X-ray analysis and 1D- and 2D-NMR spectroscopy. The complex 5 exists as 'exo'-syn-syn isomer in the solid state (Fig. 1). In solution, the same isomer exceeds with 90%. The X-ray crystal structure of 6 reveals that the dihydro(phosphinoaryl)oxazine ligand coordinates in a pseudo-enantiomeric conformation compared with that of 5 (Fig. 3). A syn-anti arrangement of the allyl substituents of 6 is favored in the solid state. H-1-NMR Spectroscopic investigations suggest that the auxiliary 6 adopts two conformations. This conformational instability together with 'exo'/'endo' and syn/anti isomerization leads to the formation of 6 isomers (Fig. 4). The asymmetric allylic substitution reaction of 1,3-diphenylallyl acetate with dimethyl malonate in the presence of 4 proceeds with a selectivity of 99% ee. The ee induced by 4 in the catalytic allylic substitution BE 1-methylbut-2-enyl acetate is moderate (54%).

  DOI：

  10.1002/1522-2675(20000607)83:6<1256::aid-hlca1256>3.0.co;2-5
• 作为产物：
  描述：

  DL-3-氨基-3-苯基丙酸 在 sodium tetrahydroborate 、 硫酸 、 zinc(II) chloride 作用下， 以 四氢呋喃 、 乙醚 、 氯苯 为溶剂， 反应 94.0h， 生成 (+/-)-2-[2-(diphenylphosphino)phenyl]-5,6-dihydro-4-phenyl-4H-1,3-oxazine
  参考文献：
  名称：

  摘要：

  The novel chiral P,N-ligand 2-[2-(diphenylphosphino)phenyl]-5,6-dihydro-4-phenyl-4H-1,3-oxazine (4) was synthesized. The corresponding {dihydro[(phosphino-xP)aryl]oxazine-xN} (eta(3)-diphenylallyl)palladium(II) hexafluorophosphate 5 and the analogous [Pd(eta(3)-1,3-dimethylallyl)] complex 6 were investigated by X-ray analysis and 1D- and 2D-NMR spectroscopy. The complex 5 exists as 'exo'-syn-syn isomer in the solid state (Fig. 1). In solution, the same isomer exceeds with 90%. The X-ray crystal structure of 6 reveals that the dihydro(phosphinoaryl)oxazine ligand coordinates in a pseudo-enantiomeric conformation compared with that of 5 (Fig. 3). A syn-anti arrangement of the allyl substituents of 6 is favored in the solid state. H-1-NMR Spectroscopic investigations suggest that the auxiliary 6 adopts two conformations. This conformational instability together with 'exo'/'endo' and syn/anti isomerization leads to the formation of 6 isomers (Fig. 4). The asymmetric allylic substitution reaction of 1,3-diphenylallyl acetate with dimethyl malonate in the presence of 4 proceeds with a selectivity of 99% ee. The ee induced by 4 in the catalytic allylic substitution BE 1-methylbut-2-enyl acetate is moderate (54%).

  DOI：

  10.1002/1522-2675(20000607)83:6<1256::aid-hlca1256>3.0.co;2-5