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.

有了这个奖项，化学合成计划是支持教授蒂莫西·拉什在伊利诺伊州州立大学探索卟啉类大环化合物的合成，表征和反应。 卟啉类化合物是一类大环杂环化合物，具有许多重要的性质，在材料科学、催化和医药等领域有着广泛的应用。卟啉作为酶的催化位点在自然界中广泛分布。 关于类似卟啉的大环化合物或类卟啉的研究报道少得多，尽管这些系统表现出与真正卟啉互补的性质。这项研究将导致更有效的路线carbaporphyrinoid系统，其中一个氮被碳取代，也将提供获得新类别的卟啉类似物。这些项目将提高我们对芳香性等基本化学概念的理解。这些新的卟啉类化合物可用于制备精细化学品，因为金属化衍生物可用于构建化学合成催化剂。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学治疗中具有潜在的医药应用价值。这些项目为培养本科生和硕士提供了良好的环境。在有机合成领域的研究生水平。 学生将接触到现代科学研究的多学科性质。在这项研究中，将开发新的碳卟啉和相关卟啉类化合物的合成路线，包括“新混淆”卟啉，碳杂卟啉和二碳卟啉。[3 + 1]-变体在MacDonald反应中的进一步应用将允许合成具有吡喃酮、非那烯、芘和苯并[f]茚单元的卟啉类化合物，并且这些研究将扩展到稠合碳卟啉类化合物二聚体的制备。一种新的合成方法carbaporphyrinoids也将开发使用卡巴三吡啉中间体。这一战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。迄今为止，对氨甲酰氯的研究很少，也将开发新的合成二氢卟啉类化合物的途径。氨甲酰氯本身具有有用的特性，也可作为碳卟啉的前体。此外，将使用碱催化的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体系。这个新的收集的大环化合物的性质将进行调查。