N-(2-diphenylphosphanyl-1-phenylethyl)-2,6-di(propan-2-yl)aniline | 746604-80-8

• 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: N-(2-diphenylphosphanyl-1-phenylethyl)-2,6-di(propan-2-yl)aniline
• CAS: 746604-80-8
• 化学式: C₃₂H₃₆NP
• 分子量: 465.618
• InChiKey: YPGZHGBBJOGBSB-UHFFFAOYSA-N

物化性质

• 沸点：
  581.2±50.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.5
• 重原子数：
  34
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (S(c))-di-μ-chlorobis[2-(1-aminoethyl)phenyl-C,N]dipalladium(II) 、 N-(2-diphenylphosphanyl-1-phenylethyl)-2,6-di(propan-2-yl)aniline 以 四氢呋喃 为溶剂， 以36%的产率得到[PdCl((S)-phenylethylamine(-1H)-κ2-C,N)(Ph2PCH2CH(Ph)NH(2,6-C6H3(i-Pr)2)-κ1-P)]
  参考文献：
  名称：

  β-氨基膦与手性环戊酸酯配合物的拆分

  摘要：

  的分辨率外消旋手性β-氨基膦博士2 PCH 2 CH（PH）NH（AR）（大号1作为Ar = C 6 H ^ 5和大号2在Ar = 2,6-C 6 H ^ 3我镨2已通过使用不同的环palpalated配合物作为手性剂进行了研究。所得的复合物以1：1的比例提供非对映异构体加合物。从乙醇中连续结晶后，一种氨基膦钯配合物的de达到98％，而从氯化溶剂中结晶后没有获得明显的de。X射线结构分析指出了P，N配体与氯离子之间的分子间氢相互作用N–H⋯Cl，这是非对映异构体加合物的形成和稳定的原因。因此，使用含氧溶剂可通过其更强的供体特性消除此类氢相互作用，并使非对映异构体分离成为可能，从而分离出光学纯的（R）-Ph 2 PCH2 CH（Ph）NH（Ph）L 1，其绝对构型已从相关的二氯化钯配合物的X射线结构分析中确定。

  DOI：

  10.1016/j.jorganchem.2005.01.023
• 作为产物：
  描述：

  N-benzylidene-2,6-diisopropylaniline 、 二苯基甲氧基膦 在 正丁基锂 、 四甲基乙二胺 作用下， 以 正己烷 、 四氢呋喃 为溶剂， 以59%的产率得到N-(2-diphenylphosphanyl-1-phenylethyl)-2,6-di(propan-2-yl)aniline
  参考文献：
  名称：

  Allylpalladium( II ) Complexes with Aminophosphane Ligands: Solution Behaviour and X‐ray Structure of cis ‐[Pd(η ³ ‐CH ₂ CHCHPh){Ph ₂ PCH ₂ CHPhNH(2,6‐C ₆ H ₃ i Pr ₂ )}][PF ₆ ]

  摘要：

  AbstractA new β‐aminophosphane L2 [Ph2PCH2CH(Ph)NH(2,6‐C6H3iPr2)], bearing an asymmetric carbon atom and a vicinal prochiral nitrogen centre and (η3‐allyl)palladium complexes of general formula [Pd(η3‐C3H4R){η2‐Ph2PCH2CH(Ph)NHAr}][PF6] (1−6) (R = H, Me or Ph and Ar = Ph or 2,6‐C6H3iPr2) have been synthesised. NMR spectroscopic studies and a crystal structure analysis of complex 6 (R = Ph, Ar = 2,6‐C6H3iPr2) confirmed the highly diastereoselective coordination of the nitrogen atom. Because of the allyl fluxionality and the presence of asymmetric centres, all the complexes exist in solution as mixtures of up to four diastereomers. For the monosubstituted allyl complexes [Pd(η3‐C3H4R){Ph2PCH2CH(Ph)NHAr}][PF6] (3−6, R = Me or Ph) only cis/trans‐P and endo/exo isomers with syn‐oriented allyl substituents have been observed in solution. The diastereomeric distribution is subject to a steric control since a modification of the steric bulk of the allyl substituents and/or N‐aryl groups strongly affect the isomers ratio. An X‐ray diffraction study of compound 6 reveals a mixture of endo and exo cis‐P syn isomers and corresponds to the first cis‐P isomer crystal structure for an N,P‐ligand allyl complex. A phase‐sensitive 2‐D NOESY NMR analysis showed that complex 1 undergoes a selective syn‐anti exchange isomerisation, involving exclusively a trans‐P opening of the η3‐allyl moiety. Therefore, η3‐η1‐η3 rearrangements in allylic complexes 1−6 were assumed to occur via the regioselective formation of a σ‐allyl intermediate. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

  DOI：

  10.1002/ejic.200300627

文献信息

• Allylpalladium( <scp>II</scp> ) Complexes with Aminophosphane Ligands: Solution Behaviour and X‐ray Structure of <i>cis</i> ‐[Pd(η ³ ‐CH ₂ CHCHPh){Ph ₂ PCH ₂ CHPhNH(2,6‐C ₆ H ₃ <i>i</i> Pr ₂ )}][PF ₆ ]
  作者：Jean‐Michel Camus、Jacques Andrieu、Philippe Richard、Rinaldo Poli

  DOI：10.1002/ejic.200300627

  日期：2004.3

  AbstractA new β‐aminophosphane L2 [Ph2PCH2CH(Ph)NH(2,6‐C6H3iPr2)], bearing an asymmetric carbon atom and a vicinal prochiral nitrogen centre and (η3‐allyl)palladium complexes of general formula [Pd(η3‐C3H4R)η2‐Ph2PCH2CH(Ph)NHAr}][PF6] (1−6) (R = H, Me or Ph and Ar = Ph or 2,6‐C6H3iPr2) have been synthesised. NMR spectroscopic studies and a crystal structure analysis of complex 6 (R = Ph, Ar = 2,6‐C6H3iPr2) confirmed the highly diastereoselective coordination of the nitrogen atom. Because of the allyl fluxionality and the presence of asymmetric centres, all the complexes exist in solution as mixtures of up to four diastereomers. For the monosubstituted allyl complexes [Pd(η3‐C3H4R)Ph2PCH2CH(Ph)NHAr}][PF6] (3−6, R = Me or Ph) only cis/trans‐P and endo/exo isomers with syn‐oriented allyl substituents have been observed in solution. The diastereomeric distribution is subject to a steric control since a modification of the steric bulk of the allyl substituents and/or N‐aryl groups strongly affect the isomers ratio. An X‐ray diffraction study of compound 6 reveals a mixture of endo and exo cis‐P syn isomers and corresponds to the first cis‐P isomer crystal structure for an N,P‐ligand allyl complex. A phase‐sensitive 2‐D NOESY NMR analysis showed that complex 1 undergoes a selective syn‐anti exchange isomerisation, involving exclusively a trans‐P opening of the η3‐allyl moiety. Therefore, η3‐η1‐η3 rearrangements in allylic complexes 1−6 were assumed to occur via the regioselective formation of a σ‐allyl intermediate. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
• Resolution of β-aminophosphines with chiral cyclopalladated complexes
  作者：Jean-Michel Camus、Patricia Roy Garcı́a、Jacques Andrieu、Philippe Richard、Rinaldo Poli

  DOI：10.1016/j.jorganchem.2005.01.023

  日期：2005.3

  1:1 ratio. After successive crystallizations from ethanol, a d.e. of 98% was achieved for one aminophosphine palladium complex, while no significant d.e. was obtained after crystallizations from chlorinated solvents. The X-ray structure analysis has pointed out intermolecular hydrogen interactions N–H⋯Cl between the P,N ligand and the chloride ion, which are responsible for the formation and stabilization

  的分辨率外消旋手性β-氨基膦博士2 PCH 2 CH（PH）NH（AR）（大号1作为Ar = C 6 H ^ 5和大号2在Ar = 2,6-C 6 H ^ 3我镨2已通过使用不同的环palpalated配合物作为手性剂进行了研究。所得的复合物以1：1的比例提供非对映异构体加合物。从乙醇中连续结晶后，一种氨基膦钯配合物的de达到98％，而从氯化溶剂中结晶后没有获得明显的de。X射线结构分析指出了P，N配体与氯离子之间的分子间氢相互作用N–H⋯Cl，这是非对映异构体加合物的形成和稳定的原因。因此，使用含氧溶剂可通过其更强的供体特性消除此类氢相互作用，并使非对映异构体分离成为可能，从而分离出光学纯的（R）-Ph 2 PCH2 CH（Ph）NH（Ph）L 1，其绝对构型已从相关的二氯化钯配合物的X射线结构分析中确定。