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

随着药物治疗对新化合物的需求和电子领域等日益复杂的应用对新材料的需求不断增加，合成化学家开发这些材料的压力也在不断增加。开发新材料和新化合物的途径之一是开发新的合成途径。在这篇文章中，我们建议使用一种非常有趣的自由基，可以分离和储存，作为有机合成的底物。尽管在35年前就被发现了，但尽管它们具有丰富的结构差异，并且含有大量的杂原子，特别是氮原子和氧原子，但它们从未被用作有机合成的底物。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良底物，包括聚合物、超分子（在这种情况下，以环烷为例，或者更准确地说，杂环烷）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，我们建议利用这种化学反应来制造独特的杂环嵌段共聚物，这些共聚物可以用于自组装研究，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，verdazyl自由基会与自身反应产生亚胺亚胺，亚胺亚胺可以与电子贫偶极试剂进行协同环加成反应，这已经导致了含杂环吡唑、三唑和恶二唑酮骨架的合成，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.