RUI: Carbaporphyrins, Carbachlorins and Related Conjugated Macrocycles

RUI：碳卟啉、卡巴氯林和相关共轭大环化合物

• 批准号: 1465049
• 负责人: Timothy Lash
• 金额: $ 32万
• 依托单位: Board of Trustees of Illinois State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2015
• 资助国家: 美国
• 起止时间: 2015-08-01 至 2020-02-29
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1465049&HistoricalAwards=false
• 关键词: RUI; Carbaporphyrins; Carbachlorins; Related; Conjugated

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.

凭借该奖项，化学合成项目将支持伊利诺伊州立大学 Timothy Lash 教授探索类卟啉大环化合物的合成、表征和反应性。 卟啉是大环杂环化合物，具有许多有价值的性质，在材料科学、催化和医学方面有应用。卟啉作为酶的催化位点广泛分布在自然界中。 关于类卟啉大环化合物或卟啉类化合物的研究报道要少得多，尽管这些系统表现出与真正卟啉互补的特性。这项研究将为碳卟啉系统提供更有效的途径，其中一个氮被碳取代，并且还将提供新类别的卟啉类似物的途径。这些项目将增进我们对芳香性等基本化学概念的理解。新的卟啉类化合物可能在精细化学品的制备中得到应用，因​​为金属化衍生物可用于构建化学合成的催化剂。这项研究更广泛的影响在于这些新物质的应用和学生培训。 目标化合物作为光动力疗法中的光敏剂具有潜在的医学应用。这些项目为有机合成领域本科生和硕士研究生的培养提供了良好的环境。 学生将接触到现代科学研究的多学科性质。在这项研究中，将开发新型碳卟啉和相关卟啉类化合物的合成路线，包括“新混淆”卟啉、碳二氢卟啉和二碳卟啉类化合物。 [3 + 1]-变体在麦克唐纳反应中的进一步应用将允许合成具有吡喃酮、苯那烯、芘和苯并[f]茚单元的类卟啉，并且这些研究将扩展到稠合的碳卟啉二聚体的制备。还将利用卡巴三吡林中间体开发一种新的碳卟啉类化合物合成方法。该策略将允许更直接地从茚或环戊二烯开始获得碳卟啉、杂碳卟啉和二碳卟啉。迄今为止，碳二氢化合物的研究还很少，二氢卟啉类化合物的新路线也将被开发。卡巴氯林本身就具有有用的特性，也可以作为碳卟啉的前体。此外，将使用碱催化MacDonald [2 + 2]方法研究adj-二碳卟啉的合成，并尝试制备三碳卟啉和四碳卟啉类系统。将研究这个新的大环化合物集合的性质。