3-(4-methoxy-phenyl)-pyrrolo[2,1-a]isoquinoline-1,2-dicarboxylic acid dimethyl ester

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: 3-(4-methoxy-phenyl)-pyrrolo[2,1-a]isoquinoline-1,2-dicarboxylic acid dimethyl ester
• 英文别名: Dimethyl 3-(4-methoxyphenyl)pyrrolo[2,1-a]isoquinoline-1,2-dicarboxylate
• 化学式: C₂₃H₁₉NO₅
• 分子量: 389.408
• InChiKey: IFHCSRDBSIGVFR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  29
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  66.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  、 丁炔二酸二甲酯 在 lithium hexamethyldisilazane 、 三甲基氯硅烷 作用下， 生成 3-(4-methoxy-phenyl)-pyrrolo[2,1-a]isoquinoline-1,2-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  Horner−Wadsworth−Emmons Reagents as Azomethine Ylide Analogues: Pyrrole Synthesis via (3 + 2) Cycloaddition

  摘要：

  Amido-substituted Horner-Wadsworth-Emmons reagents can serve as precursors to 1,3-dipoles for use in cycloaddition. These compounds are assembled in one pot via the TMSOTf-catalyzed Arbuzov reaction of imines, acid chlorides, and phosphites. The coupling of this synthesis with alkyne cycloaddition provides a three-component synthesis of pyrroles. The dipoles can be prepared with a diverse range of imines and acid chlorides, and (3 + 2) cycloaddition with unsymmetrical alkynes is highly regiospecific, providing a modular approach to form substituted pyrroles.

  DOI：

  10.1021/ol102075y

文献信息

• Phospha-Münchnones: Electronic Structures and 1,3-Dipolar Cycloadditions
  作者：Daniel J. St-Cyr、Marie S. T. Morin、Francine Bélanger-Gariépy、Bruce A. Arndtsen、Elizabeth H. Krenske、K. N. Houk

  DOI：10.1021/jo1008383

  日期：2010.6.18

  The reaction of imines, acid chlorides, PR3, and base generates a new class of 1,3-dipoles: phospha-Münchnones. These 1,3-dipoles can undergo cycloadditions with alkynes followed by loss of phosphine oxides to form pyrroles. Cycloaddition reactivity is dependent upon the PR3 employed, with PhP(catechyl) (catechyl = o-O2C6H4) providing the most rapid cycloadditions and optimal pyrrole yields. 1H, 13C

  亚胺，酰氯，PR 3和碱的反应生成一类新的1,3-偶极子：phospha-Münchnones。这些1,3-偶极子可以与炔烃进行环加成反应，然后损失氧化膦形成吡咯。环加成反应性取决于所采用的PR 3，其中PhP（catechyl）（catechyl = o -O 2 C 6 H 4）提供最快的环加成反应和最佳的吡咯产率。1 H，13 C和311 H NMR分析和计算表明，贫电子的炔丙基取代的亚膦酸酯和亚磷酸酯倾向于环状的1，3-偶极结构，而更多的富电子膦则更倾向于价互变异构的无环基价。X射线晶体学研究证实了这一点。密度泛函理论计算支持由不同PR 3引起的多种P-O相互作用并指出最有效的协同1,3-偶极环加成反应是针对那些其基态几何形状最像过渡态几何形状的偶极子。计算这些偶极子与带有吸电子基团的单取代炔烃的反应是通过逐步机理进行的。磷单元的存在会在1,3偶极子上产生较大的电子偏压，从而允许使
• Direct Synthesis of Pyrroles from Imines, Alkynes, and Acid Chlorides:  An Isocyanide-Mediated Reaction
  作者：Daniel J. St. Cyr、Nicolas Martin、Bruce A. Arndtsen

  DOI：10.1021/ol062773j

  日期：2007.2.1

  [reaction: see text] A direct synthesis of pyrroles from imines, acid chlorides, and alkynes mediated by isocyanides is reported. This reaction proceeds with a range of each of these three substrates, providing a method to generate families of pyrroles in high yield. Mechanistic studies suggest this process proceeds via the generation of imino analogues of munchnones, which can undergo in situ coupling

  [反应：见正文]据报道，由亚胺，亚胺，酰氯和炔烃直接合成吡咯是由异氰化物介导的。该反应在这三种底物的一定范围内进行，从而提供了一种以高收率产生吡咯家族的方法。机理研究表明，该过程是通过生成长棍素的亚氨基类似物来进行的，其可以与炔烃进行原位偶联以释放异氰酸酯并形成吡咯产物。
• Horner−Wadsworth−Emmons Reagents as Azomethine Ylide Analogues: Pyrrole Synthesis via (3 + 2) Cycloaddition
  作者：Marie S. T. Morin、Daniel J. St-Cyr、Bruce A. Arndtsen

  DOI：10.1021/ol102075y

  日期：2010.11.5

  Amido-substituted Horner-Wadsworth-Emmons reagents can serve as precursors to 1,3-dipoles for use in cycloaddition. These compounds are assembled in one pot via the TMSOTf-catalyzed Arbuzov reaction of imines, acid chlorides, and phosphites. The coupling of this synthesis with alkyne cycloaddition provides a three-component synthesis of pyrroles. The dipoles can be prepared with a diverse range of imines and acid chlorides, and (3 + 2) cycloaddition with unsymmetrical alkynes is highly regiospecific, providing a modular approach to form substituted pyrroles.