Synthesis of Highly Modified Porphyrinoid Systems

该项目将继续研究卟啉类大环化合物（包括碳卟啉）的合成、表征和反应性。 在以往的研究中，“3 + 1”的方法被开发用于制备碳卟啉类系统，这种方法将被应用于合成新的卟啉类似物与吡唑，异恶唑或相关的亚基。 将对已知的碳卟啉体系的化学进行进一步的研究，包括金属化反应。 还将开发一种新的“2 + 2”方法，用于从富烯合成adj-dicarbaporphyrinoids，并且将使用相同的策略来制备进一步修饰的卟啉结构。 此外，二茚基甲烷将被用来作为一个新的共轭大环的前体，并与两个倒吡咯环的二吡咯基甲烷将被用来制备一类新的双N-混乱卟啉。 含丙烯醛取代基的吡咯将用于合成乙烯基卟啉和sapphyrin的新实例，双丙烯醛的McMurry偶联将用于生成二脱氮卟啉。 这些新的卟啉型结构具有重要的理论意义，并将有助于深入了解寡吡咯大环化合物的芳香性。 这些结构也将允许制备具有有趣的和潜在有用的催化性能的新型有机金属衍生物。 这种类型的卟啉类似物也正在研究作为光动力疗法和治疗利什曼病的潜在药物，并且新的卟啉类化合物可能显示出显着的生物活性。 新的大环化合物将通过光谱方法进行彻底表征，并在可能的情况下获得X射线晶体结构。 有了这个奖项，有机和高分子化学计划支持教授蒂莫西D。他的研究对杂环和有机金属化学领域有重要意义，并可能导致催化和医学等多种应用。 因此，这些项目不仅为培养有机合成领域的本科生和MS级研究生提供了良好的环境，而且还使他们接触到现代科学研究的多学科性质。

This project will continue work on the synthesis, characterization, and reactivity of porphyrin-like macrocycles, including carbaporphyrins. In previous studies, a '3 + 1' methodology was developed for the preparation of carbaporphyrinoid systems, and this approach will be applied to the synthesis of new porphyrin analogues with pyrazole, isoxazole or related subunits. Further investigations will be conducted on the chemistry of known carbaporphyrinoid systems, including metalation reactions. A new '2 + 2' methodology for synthesizing adj-dicarbaporphyrinoids from fulvenes will also be developed and the same strategy will be used to prepare further modified porphyrinoid structures. In addition, diindenylmethane will be used as a precursor to novel conjugated macrocycles, and dipyrrylmethanes with two inverted pyrrole rings will be used to prepare a new class of doubly N-confused porphyrins. Pyrroles with acrylaldehyde substituents will be used to synthesize new examples of vinylogous porphyrins and sapphyrins, and McMurry coupling of bisacrylaldehydes will be used to generate dideazaporphyrins. The new porphyrin-type structures have great theoretical significance and will provide insights into the aromatic character of oligopyrrolic macrocycles. These structures will also allow the preparation of novel organometallic derivatives with interesting and potentially useful catalytic properties. Porphyrin analogues of this type are also being investigated as potential agents for photodynamic therapy and in the treatment of leishmaniasis, and the new porphyrinoids are likely to show significant biological activity. The new macrocycles will be thoroughly characterized by spectroscopic methods and, where possible, X-ray crystal structures will be obtained. With this award, the Organic and Macromolecular Chemistry Program supports Professor Timothy D. Lash of Illinois State University whose research has important implications for the fields of heterocyclic and organometallic chemistry, and may lead to applications as diverse as catalysis and medicine. Hence, these projects not only provide an excellent environment for training undergraduates and MS level graduate students in the field of organic synthesis, but they also expose them to the multidisciplinary nature of modern scientific research.