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首页> 外文学位 >I. Preparation of indolyl malonates via carbenoid insertion. II. Studies towards the synthesis of Quebrachamine and Aspidospermidine .
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I. Preparation of indolyl malonates via carbenoid insertion. II. Studies towards the synthesis of Quebrachamine and Aspidospermidine .

机译：I.通过类胡萝卜素插入制备吲哚基丙二酸酯。二。喹布拉奇胺和曲霉精的合成研究。

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摘要

Indoles, when treated with methyldiazomalonate under catalysis by rhodium(II)acetate, undergo C-H and N-H insertion reactions regioselectively depending on the substitution pattern on the indole moiety. In indoles where the 3-position is unsubstituted, high yields of the C3-H insertion product were observed. In 3-alkylindoles, 2-substitution predominated, while N -methyltetrahydrocarbazole yielded the product resulting from insertion into the C6-H bond. Indoles in which the nitrogen is unprotected yield varying degrees of N-H insertion.;Syntheses of the Aspidosperma alkaloids Aspidospermidine and Quebrachamine have been investigated. Our initial approaches towards these compounds involved ring closing metathesis (RCM), intramolecular Heck cross-coupling reaction, cycloannulation of cyclopropane tethered to an indole, novel homo [3+2] cycloadditions of nitrone and cyclopropanediesters, and exhaustive hydrogenation. The latest and most promising route to these alkaloids involved an elegant cascade reactions initiated by Staudinger reaction. A single Staudinger reaction was performed and proved unsuccessful. Due to time constraint, optimization of this reaction was not possible. This result placed our synthetic effort two steps away from Quebrachamine, and with few slight modifications, this route can be employed towards the syntheses of Aspidospermidine and Goniomitine.
机译：吲哚类化合物，在乙酸铑（II）的催化下，用二氮杂马来酸甲酯处理时，会根据吲哚部分的取代方式进行区域选择性的C-H和N-H插入反应。在3-位未被取代的吲哚中，观察到高产率的C3-H插入产物。在3-烷基吲哚中，2-取代占主导，而N-甲基四氢咔唑则由于插入C6-H键而产生产物。氮未被保护的吲哚产生不同程度的N-H插入。研究了天冬孢子生物碱天冬酰胺和奎布拉明的合成。我们针对这些化合物的最初方法包括闭环复分解（RCM），分子内Heck交叉偶联反应，拴系到吲哚的环丙烷的环环化，硝酮和环丙烷二酯的新型均[3 + 2]环加成以及彻底氢化。这些生物碱的最新和最有希望的途径涉及由施陶丁格反应引发的优雅的级联反应。进行了一次Staudinger反应，证明没有成功。由于时间限制，无法对该反应进行优化。该结果使我们的合成努力距离Quebrachamine仅有两步之遥，并且只需稍作修改，该路线即可用于合成Aspidospermidine和Goniomitine。

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  • 作者

    Gibe, Romelo B.;

  • 作者单位

    The University of Western Ontario (Canada).;

  • 授予单位 The University of Western Ontario (Canada).;
  • 学科 Chemistry Organic.
  • 学位 Ph.D.
  • 年度 2005
  • 页码 280 p.
  • 总页数 280
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

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