Methyl tert-butyl 2-pyrrolylmalonate

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: Methyl tert-butyl 2-pyrrolylmalonate
• 英文别名: 1-tert-butyl 3-methyl 2-(1H-pyrrol-2-yl)malonate；3-O-tert-butyl 1-O-methyl 2-(1H-pyrrol-2-yl)propanedioate
• 化学式: C₁₂H₁₇NO₄
• 分子量: 239.271
• InChiKey: BIKICBARMCEEJT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  68.4
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  溴乙酸叔丁酯 在 甲基氯化镁 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 0.83h， 生成 Methyl tert-butyl 2-pyrrolylmalonate
  参考文献：
  名称：

  Highly Efficient Synthesis of Alkyl Pyrrolylacetates and Dialkyl Pyrrolylmalonates

  摘要：

  N-Pyrrolylmagnesium halides (1,2) react with alkyl bromoacetates (3a-d) in THF solution to give alkyl 2-pyrrolylacetates (5a-d) in good yields and with very high positional selectivity (C-2:C-3 greater than or equal to 25). The high regioselectivity is rationalized in terms of an increased propinquity between C-2 and the bromoacetate methylene group as a consequence of coordination between magnesium and the carbonyl oxygen of the alkylating agent, (2,5-Dimethylpyrrol-N-yl)magnesium chloride (9) and isopropyl bromoacetate (3c) gave the 3-pyrrolylacetate 10 exclusively. Alkoxycarbonylation of the dianions of the above alkyl pyrrolylacetates with alkyl chloroformates gave the corresponding dialkyl pyrrolylmalonates, two of which (16a and 19) were transformed into the dialkyl 1,2-dihydro-3H-pyrrolo[1,2-a]pyrrole-1,1-dicarboxylates (22 and 20, respectively) with 1,2-dichloroethane under phase transfer conditions. Compound 20 was converted into the powerful nonaddicting analgesic ketorolac (21).

  DOI：

  10.1021/jo00097a025

文献信息

• Highly Efficient Synthesis of Alkyl Pyrrolylacetates and Dialkyl Pyrrolylmalonates
  作者：George C. Schloemer、Robert Greenhouse、Joseph M. Muchowski

  DOI：10.1021/jo00097a025

  日期：1994.9

  N-Pyrrolylmagnesium halides (1,2) react with alkyl bromoacetates (3a-d) in THF solution to give alkyl 2-pyrrolylacetates (5a-d) in good yields and with very high positional selectivity (C-2:C-3 greater than or equal to 25). The high regioselectivity is rationalized in terms of an increased propinquity between C-2 and the bromoacetate methylene group as a consequence of coordination between magnesium and the carbonyl oxygen of the alkylating agent, (2,5-Dimethylpyrrol-N-yl)magnesium chloride (9) and isopropyl bromoacetate (3c) gave the 3-pyrrolylacetate 10 exclusively. Alkoxycarbonylation of the dianions of the above alkyl pyrrolylacetates with alkyl chloroformates gave the corresponding dialkyl pyrrolylmalonates, two of which (16a and 19) were transformed into the dialkyl 1,2-dihydro-3H-pyrrolo[1,2-a]pyrrole-1,1-dicarboxylates (22 and 20, respectively) with 1,2-dichloroethane under phase transfer conditions. Compound 20 was converted into the powerful nonaddicting analgesic ketorolac (21).