(PCy3)Ni(η2:η2-2-(2-methylallyl)benzonitrile) | 1296867-41-8

• 英文名称: (PCy3)Ni(η2:η2-2-(2-methylallyl)benzonitrile)
• CAS: 1296867-41-8
• 化学式: C₂₉H₄₄NNiP
• 分子量: 496.339
• InChiKey: OZLDMBULCWKPOC-UHFFFAOYSA-N

计算性质

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

反应信息

• 作为反应物：
  描述：

  三氟甲磺酸 、 (PCy3)Ni(η2:η2-2-(2-methylallyl)benzonitrile) 以 氘代苯 为溶剂， 生成 [(PCy₃)Ni(CH₂C₉H₆(CH₃)NH)(trifluoromethanesulfonato)]
  参考文献：
  名称：

  Intramolecular Oxidative Cyclization of Alkenes and Nitriles with Nickel(0)

  摘要：

  The use of Me2AlCl as an additive was found to allow the oxidative addition of the Ar-CN bond in 2-(2-methylallyl)benzonitrile on nickel(0) in the presence of (PBu3)-Bu-n, giving a trans-arylnickelcyanide complex. In contrast, in the presence of PCy3, the intramolecular oxidative cyclization on nickel(0) took place to afford a nickeladihydropyrrole. Without the addition of Me2AlCl, the quantitative generation of an eta(2):eta(2)-5-ene-nitrile Ni(0) species, which was definitely converted to the nickeladihydropyrrole after treatment with Me2AlCl, was observed. In addition, TfOH also promoted the oxidative cyclization of the eta(2):eta(2)-5-ene-nitrile complex to yield the corresponding five-membered aza-nickelacycle. A similar intramolecular oxidative cyclization occurred when 2-allylbenzonitrile was used in the presence of a Lewis acid, such as Me2AlCl, Me2AlOTf, and Me3SiOTf, or of TfOH to give the corresponding nickeladihydropyrroles in quantitative yield. The molecular structures of a series of nickeladihydropyrroles were unambiguously determined by means of X-ray crystallography. The nickeladihydropyrrole derived from (2-methylallyl)benzonitrile and TfOH was found to react with HSiMe2Ph at 80 degrees C to furnish a silanamine derivative. The reaction was expanded to a Ni(0)/PCy3/TfOH-catalyzed coupling reaction of 5-ene-nitrile and HSiMe2Ph, yielding the corresponding silanamine in 84% yield.

  DOI：

  10.1021/om2001603
• 作为产物：
  描述：

  bis(1,5-cyclooctadiene)nickel (0) 、 2-(2-甲基烯丙基)苯甲腈 、 三环己基膦 以 氘代苯 为溶剂， 生成 (PCy3)Ni(η2:η2-2-(2-methylallyl)benzonitrile)
  参考文献：
  名称：

  Intramolecular Oxidative Cyclization of Alkenes and Nitriles with Nickel(0)

  摘要：

  The use of Me2AlCl as an additive was found to allow the oxidative addition of the Ar-CN bond in 2-(2-methylallyl)benzonitrile on nickel(0) in the presence of (PBu3)-Bu-n, giving a trans-arylnickelcyanide complex. In contrast, in the presence of PCy3, the intramolecular oxidative cyclization on nickel(0) took place to afford a nickeladihydropyrrole. Without the addition of Me2AlCl, the quantitative generation of an eta(2):eta(2)-5-ene-nitrile Ni(0) species, which was definitely converted to the nickeladihydropyrrole after treatment with Me2AlCl, was observed. In addition, TfOH also promoted the oxidative cyclization of the eta(2):eta(2)-5-ene-nitrile complex to yield the corresponding five-membered aza-nickelacycle. A similar intramolecular oxidative cyclization occurred when 2-allylbenzonitrile was used in the presence of a Lewis acid, such as Me2AlCl, Me2AlOTf, and Me3SiOTf, or of TfOH to give the corresponding nickeladihydropyrroles in quantitative yield. The molecular structures of a series of nickeladihydropyrroles were unambiguously determined by means of X-ray crystallography. The nickeladihydropyrrole derived from (2-methylallyl)benzonitrile and TfOH was found to react with HSiMe2Ph at 80 degrees C to furnish a silanamine derivative. The reaction was expanded to a Ni(0)/PCy3/TfOH-catalyzed coupling reaction of 5-ene-nitrile and HSiMe2Ph, yielding the corresponding silanamine in 84% yield.

  DOI：

  10.1021/om2001603