RUI: Carbaporphyrins, Carbachlorins and Related Conjugated Macrocycles

通过该奖项，化学合成项目将支持伊利诺伊州立大学的Timothy Lash教授探索类卟啉大环的合成、表征和反应性。卟啉是一种大环杂环化合物，具有许多有价值的性质，在材料科学、催化和医学等领域都有广泛的应用。卟啉作为酶的催化位点广泛存在于自然界中。类卟啉大环或类卟啉的研究报告少得多，尽管这些系统显示出与真正的卟啉互补的特性。这项研究将为碳卟啉类系统提供更有效的途径，其中一个氮被碳取代，也将为新的卟啉类似物提供途径。这些项目将提高我们对芳香性等基本化学概念的理解。由于金属化衍生物可以用来构建化学合成的催化剂，新的卟啉类化合物可能在精细化学品的制备中得到应用。这项研究的更广泛影响在于这些新物质的应用和学生培训。目标化合物作为光敏剂在光动力治疗中具有潜在的药用价值。这些项目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。学生将接触到现代科学研究的多学科性质。在本研究中，将开发新型碳卟啉和相关卟啉的合成路线，包括“新混淆”卟啉、碳氯啉和双碳卟啉。[3 + 1]-变体在麦克唐纳反应上的进一步应用将允许合成具有吡喃酮、菲烯、芘和苯并[f]独立单元的卟啉类化合物，这些研究将扩展到制备融合的类碳卟啉二聚体。此外，还将开发一种利用碳卟啉中间体合成碳卟啉类化合物的新方法。这一策略将允许从茚或环戊二烯开始更直接地获得碳卟啉、杂碳卟啉和二碳卟啉。到目前为止，对氯胺类化合物的研究还很少，还将开发新的途径来合成二氢卟啉类化合物。碳氯素本身具有有用的性质，也可以作为碳卟啉的前体。此外，还将研究用碱催化MacDonald[2 + 2]方法合成邻二碳卟啉，并尝试制备三碳和四碳卟啉类化合物体系。我们将研究这一新的巨环集合的性质。

With this award, the Chemical Synthesis program is supporting Professor Timothy Lash at Illinois State University to explore the synthesis, characterization, and reactivity of porphyrin-like macrocycles. Porphyrins are large-ring heterocycles which possess many valuable properties and have applications in materials science, catalysis and medicine. Porphyrins are widely distributed in nature as catalytic sites in enzymes. Far less research has been reported on porphyrin-like macrocycles or porphyrinoids even though these systems demonstrate properties that complement those of true porphyrins. This research will lead to more efficient routes to carbaporphyrinoid systems, in which one nitrogen is replaced by carbon, and will also provide access to new classes of porphyrin analogues. These projects will improve our understanding of fundamental chemistry concepts such as aromaticity. The new porphyrinoids may find applications in the preparation of fine chemicals, since metalated derivatives can be used to construct catalysts for chemical synthesis. Broader impacts of this research lie in applications of these new substances and in student training. The target compounds have potential medicinal applications as photosensitizers in photodynamic therapy. These projects provide an excellent environment for training undergraduates and M.S.-level graduate students in the field of organic synthesis. Students will be exposed to the multidisciplinary nature of modern scientific research.In this research, synthetic routes to novel carbaporphyrins and related porphyrinoids, including "neo-confused" porphyrins, carbachlorins and dicarbaporphyrinoids, will be developed. Further application of the [3 + 1]-variant on the MacDonald reaction will allow the synthesis of porphyrinoids with pyranone, phenalene, pyrene and benz[f]indene units, and these studies will be extended to the preparation of fused carbaporphyrinoid dimers. A new synthetic approach to carbaporphyrinoids will also be developed using carbatripyrrin intermediates. This strategy will allow more direct access to carbaporphyrins, heterocarbaporphyrins and dicarbaporphyrins starting from indene or cyclopentadiene. Carbachlorins have been little studied to date, and new routes to dihydroporphyrinoids will also be developed. Carbachlorins have useful properties in their own right and may also act as precursors to carbaporphyrins. Furthermore, syntheses of adj-dicarbaporphyrins will be investigated using a base catalyzed MacDonald [2 + 2]-approach and attempts will be made to prepare tri- and tetracarbaporphyrinoid systems. The properties of this new collection of macrocycles will be investigated.