(E)-Ethyl 2-diazo-3-oxo-3-<2-((methoxyimino)methyl)phenyl>propionate | 164254-21-1

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: (E)-Ethyl 2-diazo-3-oxo-3-<2-((methoxyimino)methyl)phenyl>propionate
• 英文别名: ethyl 2-diazo-3-[2-[(E)-methoxyiminomethyl]phenyl]-3-oxopropanoate
• CAS: 164254-21-1
• 化学式: C₁₃H₁₃N₃O₄
• 分子量: 275.264
• InChiKey: FLMDKYKWPFJHGS-OVCLIPMQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  20
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  67
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  丁炔二酸二甲酯 、 (E)-Ethyl 2-diazo-3-oxo-3-<2-((methoxyimino)methyl)phenyl>propionate 在 rhodium(II) acetate dimer 作用下， 以 二氯甲烷 为溶剂， 反应 2.5h， 以93%的产率得到12-Methoxy-8-oxo-12-azatricyclo-<7.2.1.0^2,7>dodeca-2,4,6,10-tetraene-9,10,11-tricarboxylic acid 9-ethyl ester 10,11-dimethyl ester
  参考文献：
  名称：

  Synthesis of Functionalized Azomethine Ylides via the Rh(II)-Catalyzed Cyclization of .alpha.-Diazo Carbonyls onto Imino .pi.-Bonds

  摘要：

  alpha-Diazo carbonyl compounds containing an imino group in the gamma-position have been found to undergo a rhodium(II) acetate induced cyclization reaction to generate cyclic azomethine ylides. The reactive dipole undergoes a subsequent 1,3-dipolar cycloaddition with added dipolarophiles. The imino/oxime nitrogen lone pair of electrons must be properly oriented so as to interact with the rhodium carbenoid. Thus, acyclic oxime ethers which exist in the proper E-configuration readily undergo the tandem cyclization-cycloaddition reaction. In sharp contrast, the isomeric Z-oximino diazo carbonyl system does not cyclize to an azomethine ylide but rather intramolecularly inserts into the oximino C-H bond. Addition of a catalytic amount of rhodium(II) acetate to (E)-2-(diazoacetyl)benzaldehyde O-methyloxime in the presence of DMAD or N-phenylmaleimide affords a dipolar cycloadduct in high yield. When p-quinone was used as the dipolarophile, the initially formed cycloadduct was treated with acetic anhydride to give a compound containing the basic core dibenzo[a,d]cyclohepten-5,10-imine skeleton found in MK-801. Cyclic imines such as isoxazolines were particularly effective substrates for azomethine ylide formation. The rhodium(II) catalyzed reaction of 3-(4-diazo-3-oxobutyl)-5-phenyl-Delta(2)-isoxazoline with DMAD produced a 4:1 mixture of diastereomeric cycloadducts in good yield. Cyclization of the rhodium carbenoid did not occur with the aromatic isoxazole system and this is presumably due to the low basicity of the nitrogen lone pair of electrons.

  DOI：

  10.1021/jo00097a042
• 作为产物：
  描述：

  2-(dimethoxymethyl)benzaldehyde 在 盐酸 、 potassium sulfate 、 barium permanganate 、 silica gel 、 magnesium sulfate 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二氯甲烷 为溶剂， 反应 89.0h， 生成 (E)-Ethyl 2-diazo-3-oxo-3-<2-((methoxyimino)methyl)phenyl>propionate
  参考文献：
  名称：

  Synthesis of Functionalized Azomethine Ylides via the Rh(II)-Catalyzed Cyclization of .alpha.-Diazo Carbonyls onto Imino .pi.-Bonds

  摘要：

  alpha-Diazo carbonyl compounds containing an imino group in the gamma-position have been found to undergo a rhodium(II) acetate induced cyclization reaction to generate cyclic azomethine ylides. The reactive dipole undergoes a subsequent 1,3-dipolar cycloaddition with added dipolarophiles. The imino/oxime nitrogen lone pair of electrons must be properly oriented so as to interact with the rhodium carbenoid. Thus, acyclic oxime ethers which exist in the proper E-configuration readily undergo the tandem cyclization-cycloaddition reaction. In sharp contrast, the isomeric Z-oximino diazo carbonyl system does not cyclize to an azomethine ylide but rather intramolecularly inserts into the oximino C-H bond. Addition of a catalytic amount of rhodium(II) acetate to (E)-2-(diazoacetyl)benzaldehyde O-methyloxime in the presence of DMAD or N-phenylmaleimide affords a dipolar cycloadduct in high yield. When p-quinone was used as the dipolarophile, the initially formed cycloadduct was treated with acetic anhydride to give a compound containing the basic core dibenzo[a,d]cyclohepten-5,10-imine skeleton found in MK-801. Cyclic imines such as isoxazolines were particularly effective substrates for azomethine ylide formation. The rhodium(II) catalyzed reaction of 3-(4-diazo-3-oxobutyl)-5-phenyl-Delta(2)-isoxazoline with DMAD produced a 4:1 mixture of diastereomeric cycloadducts in good yield. Cyclization of the rhodium carbenoid did not occur with the aromatic isoxazole system and this is presumably due to the low basicity of the nitrogen lone pair of electrons.

  DOI：

  10.1021/jo00097a042