Vedazyl radicals as substrates for the synthesis of small molecule and polymer heterocycles.

Vedazyl 自由基作为合成小分子和聚合物杂环的底物。

• 批准号: 249799-2010
• 负责人: Georges, Michael
• 金额: $ 3.64万
• 依托单位: University of Toronto
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2012
• 资助国家: 加拿大
• 起止时间: 2012-01-01 至 2013-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=514485
• 关键词: Vedazyl; radicals; substrates; synthesis; small

As the need for new compounds for drug therapy and new materials for increasingly sophisticated applications, as for example in the field of electronics, continues, the pressures on the synthetic chemist to develop these materials continue to increase. One way of developing new materials and compounds is to develop new pathway for their synthesis. In this submission we propose the use of verdazyl radicals, a very interesting class of radicals that can be isolated and stored, as substrates for organic synthesis. Despite having being discovered over 35 years ago, verdazyl radicals have never been used as substrates for organic synthesis in spite of their wealth of structural variance, and the fact that they contain numerous hetero atoms, especially nitrogen and oxygen atoms. These structural features suggest that they could be excellent substrates for a variety of interesting and unique first generation heterocyclic compounds, both polymeric, supramolecular (in this case as exemplified by cyclophanes, or more precisely, hetereaphanes) and small molecules, which can be made to undergo unique rearrangements to provide a second generation of compounds. Most new synthetic drugs are heterocyclic compounds and the molecular scaffolds we are proposing have been found in many of these drugs. In addition we are proposing to use this chemistry to make unique heterocyclic block copolymers that could be used in self-assembly studies, presently one of the most active areas of polymer research. The recent discovery in our laboratory that verdazyl radicals will react with themselves to produce azomethine imines that can undergo concerted cycloaddition reactions with electron-poor dipolarophiles have already led to the synthesis of heterocyclic containing pyrazole, triazole and oxadiazolone backbones, backbones commonly found in many drugs.

随着对用于药物治疗的新化合物和用于日益复杂的应用（例如在电子领域中）的新材料的需求持续，合成化学家开发这些材料的压力持续增加。 开发新材料和新化合物的方法之一是开发新的合成途径。 在这篇论文中，我们提出了使用verdazyl自由基，一个非常有趣的自由基，可以分离和存储，作为有机合成的底物。尽管已经在35年前被发现，但Verdazyl自由基从未被用作有机合成的底物，尽管它们具有丰富的结构变化，并且事实上它们含有许多杂原子，特别是氮和氧原子。这些结构特征表明，它们可以是各种感兴趣的和独特的第一代杂环化合物的优异底物，所述第一代杂环化合物是聚合物、超分子（在这种情况下，如环番（cyclophanes）或更精确地，杂环番（hetereaphanes）所例示的）和小分子，其可以进行独特的重排以提供第二代化合物。 大多数新的合成药物是杂环化合物，我们提出的分子支架已经在许多这些药物中发现。 此外，我们建议使用这种化学方法来制造独特的杂环嵌段共聚物，这些共聚物可用于自组装研究，这是目前聚合物研究中最活跃的领域之一。 最近在我们的实验室发现，verdazyl自由基将与自己反应，产生甲亚胺，可以进行协同环加成反应与贫电子偶极亲已经导致合成杂环含有吡唑，三唑和恶二唑酮骨架，在许多药物中常见的骨架。