2-Diazo-N-(2-oxo-2-phenylethyl)-N-phenylmalonamic acid ethyl ester | 156115-89-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-Diazo-N-(2-oxo-2-phenylethyl)-N-phenylmalonamic acid ethyl ester
• 英文别名: (Z)-2-diazonio-1-ethoxy-3-oxo-3-(N-phenacylanilino)prop-1-en-1-olate
• CAS: 156115-89-8
• 化学式: C₁₉H₁₇N₃O₄
• 分子量: 351.362
• InChiKey: NMGQEKHVJJRNAM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.14
• 重原子数：
  26.0
• 可旋转键数：
  7.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.16
• 拓扑面积：
  100.08
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  2-Diazo-N-(2-oxo-2-phenylethyl)-N-phenylmalonamic acid ethyl ester 在 dirhodium tetraacetate 作用下， 以 苯 为溶剂， 反应 3.0h， 以77%的产率得到3-Oxo-4,6-diphenyl-3,4-dihydro-2H-<1,4>oxazine-2-carboxylic acid ethyl ester
  参考文献：
  名称：

  Ligand Effects in the Rhodium(II)-Catalyzed Reactions of .alpha.-Diazoamides. Oxindole Formation is Promoted by the Use of Rhodium(II) Perfluorocarboxamide Catalysts

  摘要：

  An improved procedure for the preparation of ethyl 2-diazomalonyl chloride ws developed which involves the reaction of ethyl diazoacetate with triphosgene. Using this diazo acid chloride, it was possible to prepare a variety of diazoamides from substituted amines. The rhodium(II)-catalyzed decomposition of these diazoamides was studied in order to probe the chemoselectivity of the carbenoid intermediates in intramolecular insertion reactions. Rhodium(II) acetate decomposition of N-benzyl-2-diazo-N-phenylmalonamic acid ethyl ester resulted in intramolecular C-H insertion to give ethyl 1,4-diphenyl-2-oxoazetidine-3-carboxylate. By changing the catalyst ligand to trifluoroacetamide, beta-lactam formation was completely suppressed in favor of the aromatic C-H insertion which produces an oxindole as the only detectable product. The competition between aliphatic and aromatic carbon-hydrogen insertion of 2-diazo-N-phenylmalonamic acid ethyl ester provides another example of ligand effectiveness in controlling chemoselectivity in dirhodium(II)-catalyzed metal carbene reactions. Thus, treatment of the N-isobutyldiazoanilide with rhodium(II) acetate results in exclusive aliphatic C-H insertion giving 4,4-dimethyl-2-oxo-1-phenylpyrrolidine-3-carboxylic acid ethyl ester, while the perfluorobutyramide ligand promotes oxidinole formation by aromatic C-H insertion. Several other rhodium(II)-catalyzed reactions were studied and were found to be highly catalyst dependent, rhodium(II) perfluorocarboxamides promoting aromatic C-H insertion, and hence oxindole formation, over O-H insertion, cyclization onto adjacent triple bonds, or cyclization to generate 1,3-dipolar intermediates.

  DOI：

  10.1021/jo00088a028
• 作为产物：
  描述：

  2-溴苯乙酮 在 三乙胺 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 12.0h， 生成 2-Diazo-N-(2-oxo-2-phenylethyl)-N-phenylmalonamic acid ethyl ester
  参考文献：
  名称：

  Ligand Effects in the Rhodium(II)-Catalyzed Reactions of .alpha.-Diazoamides. Oxindole Formation is Promoted by the Use of Rhodium(II) Perfluorocarboxamide Catalysts

  摘要：

  An improved procedure for the preparation of ethyl 2-diazomalonyl chloride ws developed which involves the reaction of ethyl diazoacetate with triphosgene. Using this diazo acid chloride, it was possible to prepare a variety of diazoamides from substituted amines. The rhodium(II)-catalyzed decomposition of these diazoamides was studied in order to probe the chemoselectivity of the carbenoid intermediates in intramolecular insertion reactions. Rhodium(II) acetate decomposition of N-benzyl-2-diazo-N-phenylmalonamic acid ethyl ester resulted in intramolecular C-H insertion to give ethyl 1,4-diphenyl-2-oxoazetidine-3-carboxylate. By changing the catalyst ligand to trifluoroacetamide, beta-lactam formation was completely suppressed in favor of the aromatic C-H insertion which produces an oxindole as the only detectable product. The competition between aliphatic and aromatic carbon-hydrogen insertion of 2-diazo-N-phenylmalonamic acid ethyl ester provides another example of ligand effectiveness in controlling chemoselectivity in dirhodium(II)-catalyzed metal carbene reactions. Thus, treatment of the N-isobutyldiazoanilide with rhodium(II) acetate results in exclusive aliphatic C-H insertion giving 4,4-dimethyl-2-oxo-1-phenylpyrrolidine-3-carboxylic acid ethyl ester, while the perfluorobutyramide ligand promotes oxidinole formation by aromatic C-H insertion. Several other rhodium(II)-catalyzed reactions were studied and were found to be highly catalyst dependent, rhodium(II) perfluorocarboxamides promoting aromatic C-H insertion, and hence oxindole formation, over O-H insertion, cyclization onto adjacent triple bonds, or cyclization to generate 1,3-dipolar intermediates.

  DOI：

  10.1021/jo00088a028

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.