5-(3-bromophenylamino)pentan-1-ol

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 5-(3-bromophenylamino)pentan-1-ol
• 英文别名: 5-(3-bromoanilino)pentan-1-ol
• 化学式: C₁₁H₁₆BrNO
• 分子量: 258.158
• InChiKey: BXVWCQNRWVVEBH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  32.3
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  5-氨基-1-戊醇 、 1-溴-3-碘苯 在 copper(l) iodide 、 2-(2-甲基-1-氧代丙烷)环己酮 、 caesium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 7.0h， 以97%的产率得到5-(3-bromophenylamino)pentan-1-ol
  参考文献：
  名称：

  Computational Explorations of Mechanisms and Ligand-Directed Selectivities of Copper-Catalyzed Ullmann-Type Reactions

  摘要：

  Computational investigations of ligand-directed selectivities in Ullmann-type coupling reactions of methanol and methylamine with iodobenzene by beta-diketone- and 1,10-phenanthroline-ligated Cu-I complexes are reported. Density functional theory calculations using several functionals were performed on both the nucleophile formation and aryl halide activation steps of these reactions. The origin of ligand-directed selectivities in N- versus O-arylation reactions as described in a previous publication (J. Am. Chem. Soc. 2007, 129, 3490-3491) were studied and explained. The selectivities observed experimentally are derived not from initial Cu-I(nucleophile) complex formation but from the subsequent steps involving aryl halide activation. The arylation may occur via single-electron transfer (SET) or iodine atom transfer (IAT), depending on the electron-donating abilities of the ligand and nucleophile. Mechanisms involving either oxidative addition/reductive elimination or sigma-bond metathesis are disfavored. SET mechanisms are favored in reactions promoted by the beta-diketone ligand; N-arylation is predicted to be favored in these cases, in agreement with experimental results. The phenanthroline ligand promotes O-arylation reactions via IAT mechanisms in preference to N-arylation reactions, which occur via SET mechanisms; this result is also in agreement with experimental results.

  DOI：

  10.1021/ja100739h

文献信息

• N- versus O-Arylation of Aminoalcohols:  Orthogonal Selectivity in Copper-Based Catalysts
  作者：Alexandr Shafir、Phillip A. Lichtor、Stephen L. Buchwald

  DOI：10.1021/ja068926f

  日期：2007.3.1

  Two complementary protocols for copper-catalyzed arylation of aminoalcohols were developed. Selective N-arylation was accomplished at room temperature using 2-isobutyrylcyclohexanone (a beta-diketone) as supporting ligand, while selective O-arylation required the use of 3,4,7,8-tetramethylphenanthroline at 80-110 degrees C. Systematic examination of the reaction scope revealed that high levels of selectivity are achieved for a variety of substrates, provided that nonchelating (or weakly chelating) aminoalcohols are used. The generality of the method was highlighted by the synthesis, in a pairwise fashion, of a number of functionalized N- and O-arylated aminoalcohols.
• Computational Explorations of Mechanisms and Ligand-Directed Selectivities of Copper-Catalyzed Ullmann-Type Reactions
  作者：Gavin O. Jones、Peng Liu、K. N. Houk、Stephen L. Buchwald

  DOI：10.1021/ja100739h

  日期：2010.5.5

  Computational investigations of ligand-directed selectivities in Ullmann-type coupling reactions of methanol and methylamine with iodobenzene by beta-diketone- and 1,10-phenanthroline-ligated Cu-I complexes are reported. Density functional theory calculations using several functionals were performed on both the nucleophile formation and aryl halide activation steps of these reactions. The origin of ligand-directed selectivities in N- versus O-arylation reactions as described in a previous publication (J. Am. Chem. Soc. 2007, 129, 3490-3491) were studied and explained. The selectivities observed experimentally are derived not from initial Cu-I(nucleophile) complex formation but from the subsequent steps involving aryl halide activation. The arylation may occur via single-electron transfer (SET) or iodine atom transfer (IAT), depending on the electron-donating abilities of the ligand and nucleophile. Mechanisms involving either oxidative addition/reductive elimination or sigma-bond metathesis are disfavored. SET mechanisms are favored in reactions promoted by the beta-diketone ligand; N-arylation is predicted to be favored in these cases, in agreement with experimental results. The phenanthroline ligand promotes O-arylation reactions via IAT mechanisms in preference to N-arylation reactions, which occur via SET mechanisms; this result is also in agreement with experimental results.