2-(2-Carbomethoxyethyl)-1-methylpyrrole | 69917-85-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 2-(2-Carbomethoxyethyl)-1-methylpyrrole
• 英文别名: 3-(1-Methyl-2-pyrrolyl)-propionsaeuremethylester；3-(1-methyl-pyrrol-2-yl)-propionic acid methyl ester；methyl 3-(1-methylpyrrol-2-yl)propanoate
• CAS: 69917-85-7
• 化学式: C₉H₁₃NO₂
• 分子量: 167.208
• InChiKey: BOYJQMTZICRVIU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  31.2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  丙烯酸甲酯（MA） 、 alkaline earth salt of/the/ methylsulfuric acid 生成 2-(2-Carbomethoxyethyl)-1-methylpyrrole
  参考文献：
  名称：

  .beta.-Electrophilic Additions of Pentaammineosmium(II) .eta.2-Pyrrole Complexes

  摘要：

  The reactivity of a series of pyrrole complexes of the form [Os(NH3)(5)(4,5-eta(2)-L)](2+)(OTf)(2) (L = pyrrole and alkylated pyrroles) is surveyed with various electrophiles. The pyrrole ligand undergoes alkylation or acylation with a wide variety of electrophiles (e.g., acids, alkyl triflates, anhydrides, aldehydes, ketones, and Michael accepters) predominately at the -position. Depending on reaction conditions, the resulting products are either beta-substituted 1H-pyrrole or 3H-pyrrolium complexes, the latter of which resist rearomatization due to the electron-donating properties of the metal. In all cases observed, the initial addition of the electrophile occurs on the ring face anti to osmium coordination. The osmium(II)-4,5-eta(2)-pyrrole complexes are each in dynamic equilibrium with a minor isomer where the metal binds across C(3) and C(4). In this form, the uncoordinated portion of the pyrrole ring resembles an azomethine ylide, which can undergo a 1,3-dipolar cycloaddition reaction with certain electrophiles. The resulting 7-azanorbornene complexes may be ring-opened with Lewis acids to generate a-substituted 2H-pyrrolium complexes. As with the 3H-pyrrolium species, the 2H-pyrrolium complexes are stabilized by metal coordination and thereby resist rearomatization. The selectivity between Michael addition and dipolar cycloaddition depends on the pyrrole, electrophile, solvent, temperature, the presence of Lewis acids, and in some cases, concentration. The iminium carbon of both 2H- and 3H-pyrrolium tautomers is considerably less electrophilic than its organic analogs, but readily undergoes borohydride reduction to form complexes of 3- and 2-pyrrolines, respectively. When pyrrole complexes are combined with alkyne Michael accepters, the intermediate enolate can be trapped by the iminium carbon of the 3H-pyrrolium species in DMSO to form a metalated cyclobutene derivative. Decomplexation of most pyrrole and S-pyrroline derivatives can be accomplished in good yield either by heating or by oxidation of the metal (Ce-IV or DDQ). Complexes of 2-pyrrolines are considerably more difficult to remove from the metal; however, quaternization or acylation of the nitrogen facilitates their decomplexation.

  DOI：

  10.1021/jo00112a037

文献信息

• .eta.2-Pyrrole complexes as synthons to alkaloid derivatives
  作者：L. Mark Hodges、Javier Gonzalez、Jason I. Koontz、William H. Myers、W. D. Harman

  DOI：10.1021/jo00070a006

  日期：1993.8

  Eta2-Pyrrole complexes, readily generated from the corresponding pyrrole and Os(NH3)5(OTf)3, are combined with Michael acceptors under appropriate conditions to yield selectively alpha- or beta-substituted 1H-pyrroles or 7-azabicyclo [ 2.2.1] heptanes.