3-tert-butoxy-4-bromobenzonitrile | 1369898-90-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 3-tert-butoxy-4-bromobenzonitrile
• 英文别名: 3-tert-Butoxy-4-bromobenzonitrile；4-bromo-3-[(2-methylpropan-2-yl)oxy]benzonitrile
• CAS: 1369898-90-7
• 化学式: C₁₁H₁₂BrNO
• 分子量: 254.126
• InChiKey: AFXUFMMOFMVQMC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  33
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-tert-butoxy-4-bromobenzonitrile 在 palladium diacetate 、 tricyclohexylphosphine tetrafluoroborate caesium carbonate 、 三甲基乙酸 作用下， 以 均三甲苯 为溶剂， 反应 12.0h， 以78%的产率得到2,3-dihydro-2,2-dimethylbenzofuran-6-carbonitrile
  参考文献：
  名称：

  High-Yielding Palladium-Catalyzed Intramolecular Alkane Arylation:  Reaction Development and Mechanistic Studies

  摘要：

  Palladium-catalyzed alkane arylation reactions with aryl halides are described for the preparation of 2,2-dialkyl-dihydrobenzofuran substrates. These reactions occur in excellent yield and very high selectivity for the formation of one sole product arising from a reaction at nearby methyl groups. Mechanistic and computational studies point to the involvement of a concerted, inner-sphere palladation-deprotonation pathway that is enabled by the presence of three-center agostic interactions at the transition state. This mechanism accurately predicts the experimentally observed kinetic isotope effect as well as the site selectivity and should be useful in the design of new reactions and catalysts.

  DOI：

  10.1021/ja076588s
• 作为产物：
  描述：

  4-溴-3-氟苯腈 、 potassium tert-butylate 以 N,N-二甲基甲酰胺 为溶剂， 以81%的产率得到3-tert-butoxy-4-bromobenzonitrile
  参考文献：
  名称：

  High-Yielding Palladium-Catalyzed Intramolecular Alkane Arylation:  Reaction Development and Mechanistic Studies

  摘要：

  Palladium-catalyzed alkane arylation reactions with aryl halides are described for the preparation of 2,2-dialkyl-dihydrobenzofuran substrates. These reactions occur in excellent yield and very high selectivity for the formation of one sole product arising from a reaction at nearby methyl groups. Mechanistic and computational studies point to the involvement of a concerted, inner-sphere palladation-deprotonation pathway that is enabled by the presence of three-center agostic interactions at the transition state. This mechanism accurately predicts the experimentally observed kinetic isotope effect as well as the site selectivity and should be useful in the design of new reactions and catalysts.

  DOI：

  10.1021/ja076588s

文献信息

• High-Yielding Palladium-Catalyzed Intramolecular Alkane Arylation:  Reaction Development and Mechanistic Studies
  作者：Marc Lafrance、Serge I. Gorelsky、Keith Fagnou

  DOI：10.1021/ja076588s

  日期：2007.11.28

  Palladium-catalyzed alkane arylation reactions with aryl halides are described for the preparation of 2,2-dialkyl-dihydrobenzofuran substrates. These reactions occur in excellent yield and very high selectivity for the formation of one sole product arising from a reaction at nearby methyl groups. Mechanistic and computational studies point to the involvement of a concerted, inner-sphere palladation-deprotonation pathway that is enabled by the presence of three-center agostic interactions at the transition state. This mechanism accurately predicts the experimentally observed kinetic isotope effect as well as the site selectivity and should be useful in the design of new reactions and catalysts.