[(R)-BINAP]Ni(Br)(C6H4-4-CF3) | 1334746-87-0

• 英文名称: [(R)-BINAP]Ni(Br)(C6H4-4-CF3)
• CAS: 1334746-87-0
• 化学式: C₅₁H₃₆BrF₃NiP₂
• 分子量: 906.384
• InChiKey: PJSXHPDZCVTXJT-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：
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反应信息

• 作为反应物：
  描述：

  [(R)-BINAP]Ni(Br)(C6H4-4-CF3) 以 四氢呋喃 为溶剂， 以72%的产率得到([(R)-BINAP]Ni(μ-Br))2
  参考文献：
  名称：

  Nickel-Catalyzed Asymmetric α-Arylation and Heteroarylation of Ketones with Chloroarenes: Effect of Halide on Selectivity, Oxidation State, and Room-Temperature Reactions

  摘要：

  We report the alpha-arylation of ketones with a range of aryl chlorides with enantioselectivities from 90 to 99% ee catalyzed by the combination of Ni(COD)(2) and (R)-BINAP and the coupling of ketones with a range of heteroaryl chlorides with enantioselectivities up to 99% ee catalyzed by Ni(COD)(2) and (R)-DIFLUORPHOS. The analogous reactions of bromoarenes occur with much lower enantioselectivities. Mechanistic studies showed that the difference in the rates of decomposition of the arylnickel(II) halide intermediates to {[(R)-BINAP]NiX}(2) likely accounts for the difference in the enantioselectivities of the reactions of bromoarenes and chloroarenes. This catalyst decomposition can be overcome by conducting the reactions with [(R)-BINAP]Ni(eta(2)-NC-Ph) (4), which undergoes oxidative addition to haloarenes at room temperature.

  DOI：

  10.1021/ja2082087
• 作为产物：
  描述：

  对溴三氟甲苯 、 ((R)-BINAP)Ni(cod) 在 benzonitrile 作用下， 以 甲苯 为溶剂， 以80%的产率得到[(R)-BINAP]Ni(Br)(C6H4-4-CF3)
  参考文献：
  名称：

  Nickel-Catalyzed Asymmetric α-Arylation and Heteroarylation of Ketones with Chloroarenes: Effect of Halide on Selectivity, Oxidation State, and Room-Temperature Reactions

  摘要：

  We report the alpha-arylation of ketones with a range of aryl chlorides with enantioselectivities from 90 to 99% ee catalyzed by the combination of Ni(COD)(2) and (R)-BINAP and the coupling of ketones with a range of heteroaryl chlorides with enantioselectivities up to 99% ee catalyzed by Ni(COD)(2) and (R)-DIFLUORPHOS. The analogous reactions of bromoarenes occur with much lower enantioselectivities. Mechanistic studies showed that the difference in the rates of decomposition of the arylnickel(II) halide intermediates to {[(R)-BINAP]NiX}(2) likely accounts for the difference in the enantioselectivities of the reactions of bromoarenes and chloroarenes. This catalyst decomposition can be overcome by conducting the reactions with [(R)-BINAP]Ni(eta(2)-NC-Ph) (4), which undergoes oxidative addition to haloarenes at room temperature.

  DOI：

  10.1021/ja2082087