| 1598463-00-3

• CAS: 1598463-00-3
• 化学式: C₄₃H₇₀ClF₃NiP₂
• 分子量: 800.115
• InChiKey: KPFXFUMQWBXOFU-UHFFFAOYSA-M

计算性质

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

反应信息

• 作为反应物：
  描述：

  、 potassium hydroxide 以 四氢呋喃 、 水 为溶剂， 反应 18.0h， 以95%的产率得到
  参考文献：
  名称：

  Nickel Hydroxo Complexes as Intermediates in Nickel-Catalyzed Suzuki–Miyaura Cross-Coupling

  摘要：

  The synthesis, characterization, and reactivity of intermediates formed in the Ni-catalyzed Suzuki-Miyaura cross-coupling (SMC) of an aryl chloride are described. Oxidative addition of 1-chloro-4-trifluoromethylbenzene (1) to a mixture of Ni(cod)(2) and PCy3 afforded NiCl(4-CF3Ph)(PCy3)(2) (2), which then cleanly provided dimeric [Ni(4-CF3Ph)(mu-OH)-(PCy3)](2) (3) by reaction with aqueous KOH. Reactivity studies of 2 and 3 with phenylboronic acid (4) revealed that, while 2 affords only traces of the biphenyl coupling product after 24 h, the same reaction with 3 is complete within minutes at room temperature. In contrast, the reaction of 3 with potassium phenyltrihydroxyborate (6) is much slower than that with boronic acid 4, and significantly lower yields of the cross-coupling product are obtained. We show that formation of the hydroxo species 3 is the rate-determining step in the present SMC.

  DOI：

  10.1021/om5001327
• 作为产物：
  描述：

  bis(1,5-cyclooctadiene)nickel (0) 、 对氯三氟甲苯 、 三环己基膦 以 四氢呋喃 为溶剂， 反应 18.0h， 以71%的产率得到
  参考文献：
  名称：

  Nickel Hydroxo Complexes as Intermediates in Nickel-Catalyzed Suzuki–Miyaura Cross-Coupling

  摘要：

  The synthesis, characterization, and reactivity of intermediates formed in the Ni-catalyzed Suzuki-Miyaura cross-coupling (SMC) of an aryl chloride are described. Oxidative addition of 1-chloro-4-trifluoromethylbenzene (1) to a mixture of Ni(cod)(2) and PCy3 afforded NiCl(4-CF3Ph)(PCy3)(2) (2), which then cleanly provided dimeric [Ni(4-CF3Ph)(mu-OH)-(PCy3)](2) (3) by reaction with aqueous KOH. Reactivity studies of 2 and 3 with phenylboronic acid (4) revealed that, while 2 affords only traces of the biphenyl coupling product after 24 h, the same reaction with 3 is complete within minutes at room temperature. In contrast, the reaction of 3 with potassium phenyltrihydroxyborate (6) is much slower than that with boronic acid 4, and significantly lower yields of the cross-coupling product are obtained. We show that formation of the hydroxo species 3 is the rate-determining step in the present SMC.

  DOI：

  10.1021/om5001327
• 作为试剂：
  描述：

  potassium phenyltrihydroxyborate 、 对氯三氟甲苯 在 potassium phosphate monohydrate 、 C₄₃H₇₀ClF₃NiP₂ 作用下， 以 四氢呋喃 为溶剂， 生成 4-三氟甲基联苯
  参考文献：
  名称：

  Nickel Hydroxo Complexes as Intermediates in Nickel-Catalyzed Suzuki–Miyaura Cross-Coupling

  摘要：

  The synthesis, characterization, and reactivity of intermediates formed in the Ni-catalyzed Suzuki-Miyaura cross-coupling (SMC) of an aryl chloride are described. Oxidative addition of 1-chloro-4-trifluoromethylbenzene (1) to a mixture of Ni(cod)(2) and PCy3 afforded NiCl(4-CF3Ph)(PCy3)(2) (2), which then cleanly provided dimeric [Ni(4-CF3Ph)(mu-OH)-(PCy3)](2) (3) by reaction with aqueous KOH. Reactivity studies of 2 and 3 with phenylboronic acid (4) revealed that, while 2 affords only traces of the biphenyl coupling product after 24 h, the same reaction with 3 is complete within minutes at room temperature. In contrast, the reaction of 3 with potassium phenyltrihydroxyborate (6) is much slower than that with boronic acid 4, and significantly lower yields of the cross-coupling product are obtained. We show that formation of the hydroxo species 3 is the rate-determining step in the present SMC.

  DOI：

  10.1021/om5001327

文献信息

• 11C‐Cyanation of Aryl Fluorides via Nickel and Lithium Chloride‐Mediated C–F Bond Activation
  作者：Zhouen Zhang、Takashi Niwa、Kenji Watanabe、Takamitsu Hosoya

  DOI：10.1002/anie.202302956

  日期：——

  radiosynthetic method for [11C]aryl nitriles via nickel-mediated carbon-fluorine bond activation is reported. This method enables the efficient ipso-11C-cyanation of a broad range of aryl fluorides, including pharmaceutical drugs. Stoichiometric reactions and theoretical studies indicate that LiCl greatly promotes the oxidative addition of aryl fluorides to a nickel(0) complex, affording aryl(chloro)nickel(II)

  报道了通过镍介导的碳-氟键活化的[ 11 C] 芳基腈的放射合成方法。该方法能够有效地对范围广泛的芳基氟化物（包括药物）进行ipso - 11 C-氰化。化学计量反应和理论研究表明，LiCl 极大地促进了芳基氟化物向镍 (0) 配合物的氧化加成，在室温下提供芳基 (氯) 镍 (II) 配合物。