2-[(diphenylphosphanyl)methyl]-4-(R)-phenyl-4,5-dihydrooxazole | 577746-54-4

• 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: 2-[(diphenylphosphanyl)methyl]-4-(R)-phenyl-4,5-dihydrooxazole
• 英文别名: (4-(R)-phenyl-2-oxazoline-2-ylmethyl)diphenylphosphine；(R)-PCH2ox(Ph)；(4R)-2-[(Diphenylphosphanyl)methyl]-4-phenyl-4,5-dihydro-1,3-oxazole；diphenyl-[[(4R)-4-phenyl-4,5-dihydro-1,3-oxazol-2-yl]methyl]phosphane
• CAS: 577746-54-4
• 化学式: C₂₂H₂₀NOP
• 分子量: 345.381
• InChiKey: BQPACNSUAVUIGW-NRFANRHFSA-N

物化性质

• 沸点：
  477.3±45.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  25
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  21.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  dichloro(cycloocta-1,5-diene)palladium (II) 、 2-[(diphenylphosphanyl)methyl]-4-(R)-phenyl-4,5-dihydrooxazole 以 二氯甲烷 为溶剂， 以83%的产率得到[PdCl2((R)-PCH2ox(Ph)-κ2P,N)]
  参考文献：
  名称：

  New phosphino-oxazoline and related phosphino-iminolate palladium complexes; structure of an unusual zwitterionic dinuclear Pd(ii) complex

  摘要：

  膦-噁唑啉手性配体（4-(R)-苯基-2-噁唑啉-2-基甲基）二苯基膦（简称 (R)-PCH2oxPh）与 [Pd(dmba-C、N）（μ-Cl）]2 或 [PdCl2（cod）]（cod = 1,5-环辛二烯）分别生成 [Pd(dmba-C,N){(R)-PCH2oxPh-κ2P,N}]Cl 1 和 [PdCl2{(R)-PCH2oxPh-κ2P,N}] 5。钯膦-噁唑啉络合物 1 的去质子化作用发生在 PCH2 基上，并在 [Pd(dmba-C,N){(R)-PCHoxPh-κ2P,N}] 2 中形成了带有一个手性碳原子的阴离子 P,N 螯合物。2 与[Pd(dmba-C,N)(μ-Cl)]2 反应后，意外地非对映选择性地形成了双核复合物[{Pd(dmba-C,N)Cl}-(R)-{CHPPh2-(R)-oxPh}Pd(dmba-C,N)] 4。这就形成了一种非正常的齐聚物结构。在这项工作的过程中，获得了[(dmba-C,N)Pd(μ-OH)(μ-Cl)Pd(dmba-C,N)]-1/2[Pd(dmba-C,N)(μ-Cl)]27 的晶体，并对复合物 2、4-2THF、5-CH2Cl2、[PdCl(Me){(R)-PCH2oxPh-κ2P,N}] 6 和 7 进行了单晶 X 射线分析。

  DOI：

  10.1039/b300321n

文献信息

• Nickel Complexes with Oxazoline-Based <i>P</i>,<i>N</i>-Chelate Ligands:  Synthesis, Structures, and Catalytic Ethylene Oligomerization Behavior
  作者：Fredy Speiser、Pierre Braunstein、Lucien Saussine、Richard Welter

  DOI：10.1021/om034197q

  日期：2004.5.1

  The phosphinooxazoline ligands 9-12 have been prepared and used to examine and compare the catalytic properties of their corresponding Ni(II) complexes in ethylene oligomerization. The molecular structure of rac-2-[1'-(diphenylphosphanyl)ethyl]-4,4-dimethyl-4,5-dihydrooxazole (10) has been determined by X-ray diffraction. The paramagnetic Ni(II) complexes [NiX(mu-X)(P,N)](2) (19, X = Br, P,N = 2-[(diphenylphosphanyl)methyl]-4,4-dimethyl-4,5-dihydrooxazole (9)); 20, X = Cl, P,N = 9; 21, X = Cl, P,N = 10; 22, X Cl; P,N = 2-[(diphenylphosphanyl)methyl]-4-(R)-phenyl-4,5-dihydrooxazole (12); 23, X = Br, P,N = 12) and [NiCl2(P,N)] (24; P,N = 2-[1'-(diphenylphosphanyl)-1'-methylethyl]-4,4-dimethyl-4,5-dihydrooxazole (11) were prepared in yields of 79-90%, and 19 and 24 have been characterized by X-ray diffraction. The former is a dinuclear complex with distorted-trigonal-bipyramidal geometry around the Ni(II) centers, whereas 24 is a mononuclear, tetrahedral complex, which underlines the strong influence of a substituent on the carbon atom a to P. The metal coordination sphere in complexes 19-24 was determined in solution by the Evans method to be trigonal bipyramidal for 19-23 and tetrahedral for 24. Whereas complexes 19-23 and [NiCl2(PCy3)(2)] were inactive for ethylene polymerization in the presence of methylaluminoxane (MAO), the mononuclear complex 24 gave a TOF of 7900 mol of C2H4/((mol of Ni) h) with a selectivity for 1-butene of 38%. Complexes 19, 20, and 22 were inactive for the oligomerization of ethylene in the presence of NaBH4, but 19, 21, and 24 were active with AlEtCl2 as a cocatalyst. Activities and selectivities were compared to those of [NiCl2-(PCy3)(2)], a typical precatalyst used in the dimerization of alpha-olefins. Complex 19 yielded a turnover frequency of 36 300 mol of C2H4/((mol of Ni) h) in the presence of 14 equiv of AlEtCl2. In the presence of only 6 equiv of cocatalyst, the Ni complexes 21 and 24 showed TOF values of 38 100 and 45 900 mol of C2H4/((mol of Ni) h), respectively, higher than that of 27 200 mol of C2H4/((mol of Ni) h) obtained with [NiCl2(PCy3)(2)].
• New phosphino-oxazoline and related phosphino-iminolate palladium complexes; structure of an unusual zwitterionic dinuclear Pd(ii) complex
  作者：Andreas Apfelbacher、Pierre Braunstein、Luc Brissieux、Richard Welter

  DOI：10.1039/b300321n

  日期：2003.4.17

  Reaction of the phosphino-oxazoline chiral ligand (4-(R)-phenyl-2-oxazoline-2-ylmethyl)diphenylphosphine) (abbreviated (R)-PCH2oxPh) with [Pd(dmba-C,N)(μ-Cl)]2 or [PdCl2(cod)] (cod = 1,5-cyclooctadiene) led to the formation of [Pd(dmba-C,N)(R)-PCH2oxPh-κ2P,N}]Cl 1 and [PdCl2(R)-PCH2oxPh-κ2P,N}] 5, respectively. Deprotonation of the palladium phosphino-oxazoline complex 1 occurred at the PCH2 group and resulted in the formation of an anionic P,N chelate with a prochiral carbon atom in [Pd(dmba-C,N)(R)-PCHoxPh-κ2P,N}] 2. Reaction of 2 with [Pd(dmba-C,N)(μ-Cl)]2 led to the unexpected and diastereoselective formation of the dinuclear complex [Pd(dmba-C,N)Cl}-(R)-CHPPh2-(R)-oxPh}Pd(dmba-C,N)] 4 in which a Pd(dmba-C,N)Cl moiety is directly bonded to the carbon α to the P atom of the anionic P,N chelate of 2. This results in an unsual zwitterionic structure. In the course of this work, crystals of [(dmba-C,N)Pd(μ-OH)(μ-Cl)Pd(dmba-C,N)]·1/2[Pd(dmba-C,N)(μ-Cl)]27 were obtained and the single crystal X-ray analyses of complexes 2, 4·2THF, 5·CH2Cl2, [PdCl(Me)(R)-PCH2oxPh-κ2P,N}] 6 and 7 are presented.

  膦-噁唑啉手性配体（4-(R)-苯基-2-噁唑啉-2-基甲基）二苯基膦（简称 (R)-PCH2oxPh）与 [Pd(dmba-C、N）（μ-Cl）]2 或 [PdCl2（cod）]（cod = 1,5-环辛二烯）分别生成 [Pd(dmba-C,N)(R)-PCH2oxPh-κ2P,N}]Cl 1 和 [PdCl2(R)-PCH2oxPh-κ2P,N}] 5。钯膦-噁唑啉络合物 1 的去质子化作用发生在 PCH2 基上，并在 [Pd(dmba-C,N)(R)-PCHoxPh-κ2P,N}] 2 中形成了带有一个手性碳原子的阴离子 P,N 螯合物。2 与[Pd(dmba-C,N)(μ-Cl)]2 反应后，意外地非对映选择性地形成了双核复合物[Pd(dmba-C,N)Cl}-(R)-CHPPh2-(R)-oxPh}Pd(dmba-C,N)] 4。这就形成了一种非正常的齐聚物结构。在这项工作的过程中，获得了[(dmba-C,N)Pd(μ-OH)(μ-Cl)Pd(dmba-C,N)]-1/2[Pd(dmba-C,N)(μ-Cl)]27 的晶体，并对复合物 2、4-2THF、5-CH2Cl2、[PdCl(Me)(R)-PCH2oxPh-κ2P,N}] 6 和 7 进行了单晶 X 射线分析。