(R)-N-(1-(3-chlorophenyl)ethyl)-P,P-diphenylphosphinic amide | 1207166-23-1

• 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: (R)-N-(1-(3-chlorophenyl)ethyl)-P,P-diphenylphosphinic amide
• 英文别名: (1R)-1-(3-chlorophenyl)-N-diphenylphosphorylethanamine
• CAS: 1207166-23-1
• 化学式: C₂₀H₁₉ClNOP
• 分子量: 355.804
• InChiKey: GCLJTBNGKWHZSC-MRXNPFEDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  1-(3-chlorophenyl)-N-diphenylphosphorylmethanimine 、 Dimethylzinc 在 chloro(1,5-cyclooctadiene)rhodium(I) dimer 、 (-)-1,2-双[(2R,5R)-2,5-二甲基磷]苯 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 5.6h， 生成 (R)-N-(1-(3-chlorophenyl)ethyl)-P,P-diphenylphosphinic amide 、 (S)-N-(1-(3-chlorophenyl)ethyl)-P,P-diphenylphosphinamide 、 N-(3-chlorobenzyl)-P,P-diphenylphosphinic amide
  参考文献：
  名称：

  Reaction prospecting by 31P NMR: enantioselective rhodium-DuPhos catalysed addition of ZnMe2 to diphenylphosphinoylimines

  摘要：

  Chiral shift P-31 NMR spectroscopy allows the identification of ligand leads in asymmetric catalyst systems for ZnMe2 addition to ArCH=NP(C)Ph-2. Subsequent GC-based optimisation shows [RhC](CH2=CH2)(2)](2) and (RR)-MeDuPhos to be the optimal pre-catalyst combination (product in 78-93% ee). Transmetallation of [(MeDuPhos)Rh{N(P(O)Ph-2-CHMeAr}] with ZnMe2 appears to be the rate limiting step of the catalytic cycle as competing coordination by the imine starting material leads to Ph2P(O)NHCH2Ar via MVP hydrogen-transfer. This limitation can largely be overcome by the slow addition of the imine. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2009.09.020

文献信息

• Reaction prospecting by 31P NMR: enantioselective rhodium-DuPhos catalysed addition of ZnMe2 to diphenylphosphinoylimines
  作者：Rosemary H. Crampton、Samir El Hajjaji、Martin E. Fox、Simon Woodward

  DOI：10.1016/j.tetasy.2009.09.020

  日期：2009.11

  Chiral shift P-31 NMR spectroscopy allows the identification of ligand leads in asymmetric catalyst systems for ZnMe2 addition to ArCH=NP(C)Ph-2. Subsequent GC-based optimisation shows [RhC](CH2=CH2)(2)](2) and (RR)-MeDuPhos to be the optimal pre-catalyst combination (product in 78-93% ee). Transmetallation of [(MeDuPhos)RhN(P(O)Ph-2-CHMeAr}] with ZnMe2 appears to be the rate limiting step of the catalytic cycle as competing coordination by the imine starting material leads to Ph2P(O)NHCH2Ar via MVP hydrogen-transfer. This limitation can largely be overcome by the slow addition of the imine. (C) 2009 Elsevier Ltd. All rights reserved.