1-Allyl-1H-indole-2-carboxylic acid methylamide | 155193-51-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: 1-Allyl-1H-indole-2-carboxylic acid methylamide
• 英文别名: N-methyl-1-prop-2-enylindole-2-carboxamide
• CAS: 155193-51-4
• 化学式: C₁₃H₁₄N₂O
• 分子量: 214.267
• InChiKey: IQDOPZUCIUHVBH-UHFFFAOYSA-N

物化性质

• 沸点：
  446.0±28.0 °C(predicted)
• 密度：
  1.09±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  34
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-Allyl-1H-indole-2-carboxylic acid methylamide 在 dirhodium(II) tetrakis(perfluorobutyrate) 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 、 苯 为溶剂， 反应 2.08h， 生成 3-Hydroxy-1-methyl-2-oxo-2,3,4,5-tetrahydro-1H-pyrido<2',3':3,4>pyrrolo<1,2-a>indole-3-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  Studies on the Intramolecular Cycloaddition Reaction of Mesoionics Derived from the Rhodium(II)-Catalyzed Cyclization of Diazoimides

  摘要：

  A series of alkenyl-substituted imides were prepared by treating the appropriate amide with 2,2,6-trimethyl-4H-1,3-dioxen-4-one in xylene at 140-degrees-C to give the N-acetoacylated imides. Exposure of these imides to standard diazo transfer conditions gave the desired diazoimides. The carbenoid intermediate derived by treatment of the diazoimide with rhodium(II) acetate undergoes ready cyclization onto the neighboring amide carbonyl oxygen atom to generate an isomunchnone intermediate. Subsequent 1,3-dipolar cycloaddition across the pendant olefin affords the cycloadduct in high yield. The stereochemical assignment of several of the cycloadducts was deduced by X-ray crystallography. The stereochemical outcome of the reaction is the consequence of an endo cycloaddition of the neighboring pi-bond across the transient isomunchnone dipole. Molecular mechanics calculations were used to model energy differences between the endo and exo diastereomers. The calculations reveal that the endo diastereomers are significantly (8-12 kcal/mol) lower in energy than the corresponding exo isomers thereby providing a rationale for the preferred endo cycloaddition. Ring opening of the cycloadducts occurred readily producing a transient N-acyliminium ion which either lost a proton to give an enamide or was reduced by Et3SiH to afford a bicyclic piperidine ring.

  DOI：

  10.1021/jo00085a035
• 作为产物：
  描述：

  吲哚-2-羧酸乙酯 在 氢氧化钾 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 乙醇 、 水 为溶剂， 反应 59.0h， 生成 1-Allyl-1H-indole-2-carboxylic acid methylamide
  参考文献：
  名称：

  Studies on the Intramolecular Cycloaddition Reaction of Mesoionics Derived from the Rhodium(II)-Catalyzed Cyclization of Diazoimides

  摘要：

  A series of alkenyl-substituted imides were prepared by treating the appropriate amide with 2,2,6-trimethyl-4H-1,3-dioxen-4-one in xylene at 140-degrees-C to give the N-acetoacylated imides. Exposure of these imides to standard diazo transfer conditions gave the desired diazoimides. The carbenoid intermediate derived by treatment of the diazoimide with rhodium(II) acetate undergoes ready cyclization onto the neighboring amide carbonyl oxygen atom to generate an isomunchnone intermediate. Subsequent 1,3-dipolar cycloaddition across the pendant olefin affords the cycloadduct in high yield. The stereochemical assignment of several of the cycloadducts was deduced by X-ray crystallography. The stereochemical outcome of the reaction is the consequence of an endo cycloaddition of the neighboring pi-bond across the transient isomunchnone dipole. Molecular mechanics calculations were used to model energy differences between the endo and exo diastereomers. The calculations reveal that the endo diastereomers are significantly (8-12 kcal/mol) lower in energy than the corresponding exo isomers thereby providing a rationale for the preferred endo cycloaddition. Ring opening of the cycloadducts occurred readily producing a transient N-acyliminium ion which either lost a proton to give an enamide or was reduced by Et3SiH to afford a bicyclic piperidine ring.

  DOI：

  10.1021/jo00085a035

文献信息

• Ethyl 2-diazomalonyl chloride. An efficient diazoacylating reagent
  作者：Joseph P. Marino、Martin H. Osterhout、Alan T. Price、Scott M. Sheehan、Albert Padwa

  DOI：10.1016/s0040-4039(00)75980-6

  日期：1994.1

  Ethyl 2-diazomalonyl chloride readily reacts with aromatic and aliphatic amines, alcohols, thiols, and amides for form a variety of alpha-diazo carbonyl species.