(+/-)-α-Phenyl-2,5-dioxo-1H-pyrrole-1-acetic acid methyl ester | 135557-49-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (+/-)-α-Phenyl-2,5-dioxo-1H-pyrrole-1-acetic acid methyl ester
• 英文别名: Methyl 2-(2,5-dioxopyrrol-1-yl)-2-phenylacetate
• CAS: 135557-49-2
• 化学式: C₁₃H₁₁NO₄
• mdl: MFCD17442120
• 分子量: 245.235
• InChiKey: MSJGHNSMGCDJOI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.153
• 拓扑面积：
  63.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (+/-)-α-Phenyl-2,5-dioxo-1H-pyrrole-1-acetic acid methyl ester 以 1,4-二氧六环 、 甲苯 为溶剂， 反应 29.0h， 生成 (+/-)-6-Methyl-2,4-dioxo-α-phenyl-3,6-diazabicyclo<3.1.0>hexane-3-acetic acid methyl ester
  参考文献：
  名称：

  Development of an asymmetric approach to the 3,8-diazabicyclo[3.2.1]octane moiety of quinocarcin via intramolecular 1,3-dipolar cycloadditions of photochemically generated azomethine ylides

  摘要：

  Exploratory work culminating in an enantioselective approach to the DNA-reactive alkaloid quinocarcin (1) is detailed. The key step involves auxiliary-controlled dipolar cycloaddition between photochemically generated azomethine ylides such as 11 and Oppolzer's chiral acryloyl sultam (-)-32 to assemble the 6-exo-substituted 3,8-diazabicyclo[3.2.1]octane core of 1. The synthetic sequence begins with condensation of the benzylamines 3 and maleic anhydride to give the N-alkylated maleimides 6. Triazoline formation (MeN3) followed by photolytic (lambda > 3000 angstrom) extrusion of nitrogen leads to the corresponding aziridines 10. Upon irradiation at 2537 angstrom, these aziridines undergo electrocyclic ring-opening to give azomethine ylides 11, which can be trapped with (-)-32 to give the 6-exo-substituted cycloadduct 33 (diastereoselectivity, ds > 25:1). These results stand in sharp contrast to cycloadditions of 11 with (achiral and chiral) acrylate ester dipolarophiles as well as acrylonitrile, which proceed with no appreciable facial selectivity. The expected re-face selectivity of (-)-32 was confirmed in one case by X-ray crystallographic analysis of endo-adduct 35a. Removal (and recovery) of the chiral sultam auxiliary can be effected by titanium (IV)-mediated alcoholysis to give ester derivatives of the cycloadducts.

  DOI：

  10.1021/jo00020a035
• 作为产物：
  描述：

  甲基2-(苯基氨基)乙酸酯 在 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 作用下， 以 乙醚 为溶剂， 反应 58.0h， 生成 (+/-)-α-Phenyl-2,5-dioxo-1H-pyrrole-1-acetic acid methyl ester
  参考文献：
  名称：

  Development of an asymmetric approach to the 3,8-diazabicyclo[3.2.1]octane moiety of quinocarcin via intramolecular 1,3-dipolar cycloadditions of photochemically generated azomethine ylides

  摘要：

  Exploratory work culminating in an enantioselective approach to the DNA-reactive alkaloid quinocarcin (1) is detailed. The key step involves auxiliary-controlled dipolar cycloaddition between photochemically generated azomethine ylides such as 11 and Oppolzer's chiral acryloyl sultam (-)-32 to assemble the 6-exo-substituted 3,8-diazabicyclo[3.2.1]octane core of 1. The synthetic sequence begins with condensation of the benzylamines 3 and maleic anhydride to give the N-alkylated maleimides 6. Triazoline formation (MeN3) followed by photolytic (lambda > 3000 angstrom) extrusion of nitrogen leads to the corresponding aziridines 10. Upon irradiation at 2537 angstrom, these aziridines undergo electrocyclic ring-opening to give azomethine ylides 11, which can be trapped with (-)-32 to give the 6-exo-substituted cycloadduct 33 (diastereoselectivity, ds > 25:1). These results stand in sharp contrast to cycloadditions of 11 with (achiral and chiral) acrylate ester dipolarophiles as well as acrylonitrile, which proceed with no appreciable facial selectivity. The expected re-face selectivity of (-)-32 was confirmed in one case by X-ray crystallographic analysis of endo-adduct 35a. Removal (and recovery) of the chiral sultam auxiliary can be effected by titanium (IV)-mediated alcoholysis to give ester derivatives of the cycloadducts.

  DOI：

  10.1021/jo00020a035

文献信息

• Microwave-induced One-pot Synthesis of N-carboxyalkyl Maleimides and Phthalimides†
  作者：Harsha N. Borah、Romesh C. Boruah、Jagir S. Sandhu

  DOI：10.1039/a707961c

  日期：——

  Maleic and phthalic anhydride condenses with amino acids and alkylamines under microwave irradiation to afford N-substituted maleimides and phthalimides in excellent yields.

  在微波辐照下，马来酸酐和邻苯二甲酸酐与氨基酸和烷基胺发生缩合反应，生成 N-取代的马来酰亚胺和邻苯二甲酰亚胺，收率极高。
• Development of an asymmetric approach to the 3,8-diazabicyclo[3.2.1]octane moiety of quinocarcin via intramolecular 1,3-dipolar cycloadditions of photochemically generated azomethine ylides
  作者：Philip Garner、Wen Bin Ho、Sunitha K. Grandhee、Wiley J. Youngs、Vance O. Kennedy

  DOI：10.1021/jo00020a035

  日期：1991.9

  Exploratory work culminating in an enantioselective approach to the DNA-reactive alkaloid quinocarcin (1) is detailed. The key step involves auxiliary-controlled dipolar cycloaddition between photochemically generated azomethine ylides such as 11 and Oppolzer's chiral acryloyl sultam (-)-32 to assemble the 6-exo-substituted 3,8-diazabicyclo[3.2.1]octane core of 1. The synthetic sequence begins with condensation of the benzylamines 3 and maleic anhydride to give the N-alkylated maleimides 6. Triazoline formation (MeN3) followed by photolytic (lambda > 3000 angstrom) extrusion of nitrogen leads to the corresponding aziridines 10. Upon irradiation at 2537 angstrom, these aziridines undergo electrocyclic ring-opening to give azomethine ylides 11, which can be trapped with (-)-32 to give the 6-exo-substituted cycloadduct 33 (diastereoselectivity, ds > 25:1). These results stand in sharp contrast to cycloadditions of 11 with (achiral and chiral) acrylate ester dipolarophiles as well as acrylonitrile, which proceed with no appreciable facial selectivity. The expected re-face selectivity of (-)-32 was confirmed in one case by X-ray crystallographic analysis of endo-adduct 35a. Removal (and recovery) of the chiral sultam auxiliary can be effected by titanium (IV)-mediated alcoholysis to give ester derivatives of the cycloadducts.