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

随着对用于药物治疗的新化合物和用于日益复杂的应用的新材料的需求不断增加，例如在电子领域，合成化学家开发这些材料的压力继续增加。开发新材料和新化合物的一种方法是开发新的合成途径。在这份意见书中，我们建议使用绿豆素自由基，这是一类非常有趣的自由基，可以分离和存储，作为有机合成的底物。尽管人们在35年前就发现了绿豆根基，但它们从未被用作有机合成的底物，尽管它们的结构变化很大，而且它们含有大量的杂原子，特别是氮和氧原子。这些结构特征表明，它们可能是各种有趣和独特的第一代杂环化合物的优秀底物，既有聚合物、超分子(在这种情况下，如环芳烃，或者更准确地说，杂环芳烃)和小分子，它们可以经过独特的重排来提供第二代化合物。大多数新的合成药物都是杂环化合物，我们提出的分子支架已经在许多这样的药物中找到。此外，我们建议利用这种化学方法来制造独特的杂环嵌段共聚物，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。我们实验室最近发现，绿豆根基可以与自身反应生成甲亚胺类化合物，这些亚胺类化合物可以与缺乏电子的偶极分子发生协同环加成反应，从而合成了含有吡唑、三氮唑和恶二唑酮的杂环骨架，这些骨架在许多药物中都很常见。

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.