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Direct Functionalization of Heterocyclic and Non- Heterocyclic Arenes.

机译：杂环和非杂环芳烃的直接官能化。

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摘要

The application of transition metals towards direct functionalization processes has exposed an opportunistic new class of carbon-carbon bond forming reactions. Given the undeniable ubiquity of C--H bonds, the possibility of introducing functionality through direct means with minimal preactivation is an irresistible strategy in synthesis. As such one can envision rapidly and efficiently building up complex scaffolds towards complex molecules of interest in a plethora of chemical fields.;There remains a significant challenge in developing direct processes utilizing inexpensive transition metals. Furthermore, the synthesis of pharmacologically relevant 2-alkenyl pyridines through direct transformations had not yet been reported. We focused on these challenges and developed a copper-catalyzed direct alkenylation of N-iminopyridinium ylides. A novel method to prepare the vinyl iodide coupling partners will also be discussed. The scopes of these reactions are quite large and remarkably chemoselective (Chapter 3). Through the optimization of this direct process we uncovered an unique means of synthesizing 2-substituted pyrazolo[1,5-a]pyridines (Chapter 4). The global process involved a tandem direct functionalization/cyclization sequence, and may be the first account of a direct process used in a cascade. This work also solves an important problem, as the synthesis of these substrates through alternate means is not straightforward.;The last two chapters will detail direct arylation technologies that do not involve heterocyclic coupling partners. Chapter 5 will highlight our uncovering of a palladium-catalyzed, directed, umpolung arylation of benzene and other arene derivatives. This was the first account of a direct functionalization whereby the directing group is situated on the pseudo electrophile. Also, it adds to the few examples of direct benzene arylation existing in the literature. Finally, a discussion of an atom economical, inexpensive, sustainable iron-catalyzed direct arylation process will be presented with special emphasis on substrate scope and mechanistic investigations (Chapter 6).;Keywords : N-Iminopyridinium ylides, direct arylation, alkenylation, catalysis, palladium, copper, iron, directing group.;The focus of this thesis is on the direct functionalization of heterocyclic and non-heterocyclic arenes, focusing on arylation technologies. First, the topic of direct arylation will be introduced, with special emphasis being on pyridines (Chapter 1). These molecules comprise the backbone of a myriad of biologically active compounds, and are also relevant in material sciences, agrochemicals, and natural products synthesis. This will be followed by a discussion of work on the palladium-catalyzed direct arylation of N-iminopyridinium ylides with accent on the derivatization of the pyridinium following the sp2 phenylation (Chapter 2). The exploration of this process led to the discovery of direct benzylic arylation when 2-alkyl N-iminopyridinium ylides are employed as reacting partners, in addition to palladium-catalyzed Tsuji-Trost allylations, and metal-free direct alkylation via phase transfer catalysis. All of these findings will be discussed in detail.
机译：过渡金属在直接官能化过程中的应用暴露了机会主义的新型碳-碳键形成反应。鉴于C–H键无处不在，合成中不可抗拒的策略是通过直接手段以最小的预活化引入功能的可能性。因此，可以设想快速有效地在众多化学领域中构建针对感兴趣的复杂分子的复杂支架。在利用廉价的过渡金属开发直接工艺方面，仍然存在重大挑战。此外，尚未报道通过直接转化来合成药理学上相关的2-烯基吡啶。我们专注于这些挑战，并开发了铜催化的N-亚氨基吡啶鎓烷基化物的直接烯基化。还将讨论制备碘代乙烯偶合体的新方法。这些反应的范围很大，并且具有明显的化学选择性（第3章）。通过优化该直接过程，我们发现了一种合成2-取代吡唑并[1,5-a]吡啶的独特方法（第4章）。全局过程涉及串联直接功能化/环化序列，并且可能是级联中使用的直接过程的第一个说明。这项工作还解决了一个重要问题，因为通过替代方法合成这些底物并不容易。最后两章将详细介绍不涉及杂环偶联剂的直接芳基化技术。第5章将重点介绍我们发现的苯和其他芳烃衍生物的钯催化，定向，酚芳构化。这是直接官能化的第一个说明，其中引导基团位于假亲电体上。而且，它增加了文献中存在的一些直接苯芳基化的例子。最后，将对原子经济，廉价，可持续的铁催化直接芳基化过程进行讨论，并特别着重于底物范围和机理研究（第6章）;关键词：N-亚氨基吡啶鎓盐，直接芳基化，烯基化，催化，本文的重点是杂环和非杂环芳烃的直接官能化，重点是芳基化技术。首先，将介绍直接芳基化的主题，特别着重于吡啶（第1章）。这些分子构成了众多生物活性化合物的骨架，并且在材料科学，农业化学和天然产物合成中也具有重要意义。接下来将讨论有关N2亚氨基吡啶鎓钯在钯催化下直接芳基化的工作，重点是sp2苯基化后吡啶鎓的衍生化（第2章）。对这种方法的探索导致发现，除了钯催化的Tsuji-Trost烯丙基化反应以及通过相转移催化的无金属直接烷基化反应外，当使用2-烷基N-亚氨基吡啶鎓烷基化物作为反应伙伴时，可以直接进行苄基芳基化反应。所有这些发现将被详细讨论。

著录项

  • 作者

    Mousseau, James J.;

  • 作者单位

    Universite de Montreal (Canada).;

  • 授予单位 Universite de Montreal (Canada).;
  • 学科 Chemistry Organic.
  • 学位 Ph.D.
  • 年度 2011
  • 页码 341 p.
  • 总页数 341
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 肿瘤学;
  • 关键词

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