Synthesis of Highly Modified Porphyrinoid Systems

该项目将继续研究类卟啉大环的合成、表征和反应性，包括碳卟啉。在之前的研究中，我们开发了一种“3 + 1”的方法来制备类碳卟啉体系，该方法将用于合成含有吡唑、异恶唑或相关亚基的新型卟啉类似物。进一步的研究将对已知的类碳卟啉系统进行化学研究，包括金属化反应。我们还将开发一种新的“2 + 2”方法来合成邻二碳卟啉类化合物，并将采用同样的方法制备进一步修饰的卟啉类化合物结构。此外，二乙烯基甲烷将被用作新型共轭大环的前驱体，而具有两个反吡咯环的二吡基甲烷将被用于制备一类新的双n混淆卟啉。以丙烯醛为取代基的吡咯将用于合成新的葡萄状卟啉和卟啉，双丙烯醛的McMurry偶联将用于合成双二氮卟啉。新的卟啉型结构具有重要的理论意义，并将为研究低聚吡啶类大环的芳香特性提供新的思路。这些结构还将允许制备具有有趣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，新的卟啉类物质可能显示出显著的生物活性。新的大环将通过光谱方法彻底表征，并且在可能的情况下，将获得x射线晶体结构。通过这个奖项，有机和大分子化学项目支持伊利诺伊州立大学的Timothy D. Lash教授，他的研究对杂环和有机金属化学领域具有重要意义，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硕士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.