N-(2-bromo-4,6-dimethylphenyl)-2-phenylacetamide | 1429622-59-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-(2-bromo-4,6-dimethylphenyl)-2-phenylacetamide
• CAS: 1429622-59-2
• 化学式: C₁₆H₁₆BrNO
• 分子量: 318.213
• InChiKey: FIBNJYPCDDQZCL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  碘甲烷 、 N-(2-bromo-4,6-dimethylphenyl)-2-phenylacetamide 在 sodium hydride 作用下， 以 四氢呋喃 、 mineral oil 为溶剂， 反应 5.0h， 以66%的产率得到N-(2-bromo-4,6-dimethylphenyl)-N-methyl-2-phenylacetamide
  参考文献：
  名称：

  Rotational Isomers of N-Methyl-N-arylacetamides and Their Derived Enolates: Implications for Asymmetric Hartwig Oxindole Cyclizations

  摘要：

  The rotational preferences of N-(2-bromo-4,6-dimethylphenyl)-N-methyl 2-phenylpropanamide were studied as a model of precursors for Hartwig asymmetric oxindole cyclizations. The atropisomers of this compound were separated by flash chromatography, and then the enantiomers were resolved and the interconversions of the stereocenter and the N-Ar axis were studied. Under thermal conditions, the axis is very stable. Under the basic conditions of the Hartwig cyclization, both the stereocenter and the chiral axis equilibrate via enolate formation. The N-Ar rotation barrier of a 2-phenylacetamide analogue was reduced from 31 kcal mol(-1) in the precursor to 17 kcal mol(-1) in the enolate. Reasons for this dramatic barrier reduction and implications of both N-Ar and amide C-N rotations for Hartwig cyclizations are discussed.

  DOI：

  10.1021/jo400385t
• 作为产物：
  描述：

  2-溴-4,6-二甲基苯胺 、 苯乙酰氯 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以45%的产率得到N-(2-bromo-4,6-dimethylphenyl)-2-phenylacetamide
  参考文献：
  名称：

  Rotational Isomers of N-Methyl-N-arylacetamides and Their Derived Enolates: Implications for Asymmetric Hartwig Oxindole Cyclizations

  摘要：

  The rotational preferences of N-(2-bromo-4,6-dimethylphenyl)-N-methyl 2-phenylpropanamide were studied as a model of precursors for Hartwig asymmetric oxindole cyclizations. The atropisomers of this compound were separated by flash chromatography, and then the enantiomers were resolved and the interconversions of the stereocenter and the N-Ar axis were studied. Under thermal conditions, the axis is very stable. Under the basic conditions of the Hartwig cyclization, both the stereocenter and the chiral axis equilibrate via enolate formation. The N-Ar rotation barrier of a 2-phenylacetamide analogue was reduced from 31 kcal mol(-1) in the precursor to 17 kcal mol(-1) in the enolate. Reasons for this dramatic barrier reduction and implications of both N-Ar and amide C-N rotations for Hartwig cyclizations are discussed.

  DOI：

  10.1021/jo400385t

文献信息

• Asymmetric synthesis of axially chiral anilides by Pd-catalyzed allylic substitutions with P/olefin ligands
  作者：Yilin Liu、Xiangqing Feng、Haifeng Du

  DOI：10.1039/c4ob01087f

  日期：——

  synthesis of axially chiral anilides is therefore of great interest in synthetic and pharmaceutical chemistry. In this paper, a palladium-catalyzed asymmetric allylic substitution of ortho-substituted anilides using phosphorus amidite–olefin ligands was successfully achieved to afford a variety of axially chiral anilides in high yields with up to 84% ee. The absolute configurations of chiral anilides were

  作为一类有吸引力的非联芳基阻转异构化合物，C–N轴向手性苯胺受到了相当大的关注，并且已经成功开发了几种合成方法。钯催化的不对称烯丙基胺化被证明是一种有效的手性苯胺合成方法，尽管在先前的工作中仅实现了中等的对映选择性和相对窄的底物范围。因此，在合成和药物化学中，寻找用于合成轴向手性酸酐的高效方法是非常重要的。本文用钯催化邻位的不对称烯丙基取代使用磷酰胺-烯烃配体成功地实现了取代基的苯胺，以高收率提供了高达84％ee的多种轴向手性苯胺。还从X射线和CD光谱确定了手性酸酐的绝对构型。
• Rotational Isomers of <i>N</i>-Methyl-<i>N</i>-arylacetamides and Their Derived Enolates: Implications for Asymmetric Hartwig Oxindole Cyclizations
  作者：Jérémie Mandel、Xiaohong Pan、E. Ben Hay、Steven J. Geib、Craig S. Wilcox、Dennis P. Curran

  DOI：10.1021/jo400385t

  日期：2013.4.19

  The rotational preferences of N-(2-bromo-4,6-dimethylphenyl)-N-methyl 2-phenylpropanamide were studied as a model of precursors for Hartwig asymmetric oxindole cyclizations. The atropisomers of this compound were separated by flash chromatography, and then the enantiomers were resolved and the interconversions of the stereocenter and the N-Ar axis were studied. Under thermal conditions, the axis is very stable. Under the basic conditions of the Hartwig cyclization, both the stereocenter and the chiral axis equilibrate via enolate formation. The N-Ar rotation barrier of a 2-phenylacetamide analogue was reduced from 31 kcal mol(-1) in the precursor to 17 kcal mol(-1) in the enolate. Reasons for this dramatic barrier reduction and implications of both N-Ar and amide C-N rotations for Hartwig cyclizations are discussed.