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.

通过这一奖项，化学合成项目支持伊利诺伊州立大学的蒂莫西·拉什教授探索类似卟啉的大环的合成、表征和反应活性。卟啉是一类大环杂环化合物，具有许多有价值的性质，在材料科学、催化和医学等领域有着广泛的应用。在自然界中，卟啉作为酶的催化部位广泛分布。关于类似卟啉的大环或卟啉类化合物的研究报道要少得多，尽管这些系统显示出与真正的卟啉性质互补的性质。这项研究将导致更有效的途径获得碳卟啉系统，其中一个氮被碳取代，还将提供获得新类别的卟啉类似物的途径。这些项目将提高我们对芳香性等基本化学概念的理解。新的卟啉类化合物可能会在精细化学品的制备中得到应用，因为金属化衍生物可以用来构建化学合成的催化剂。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。目标化合物作为光动力疗法中的光敏剂具有潜在的医药应用前景。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。在这项研究中，将开发新的碳卟啉和相关的卟啉类化合物的合成路线，包括“新混淆”的卟啉、卡宾和二碳卟啉类化合物。进一步将[3+1]-变构体应用于MacDonald反应，将允许合成具有吡喃酮、菲、芘和苯并[f]烯单元的卟啉类化合物，这些研究将扩展到制备稠合的碳卟啉二聚体。还将开发一种新的合成碳卟啉类化合物的方法，该方法使用碳三联吡咯中间体。这一战略将允许从吲哚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，对三氯甲烷的研究还很少，二氢卟啉类化合物的新路线也将被开发出来。Carbachlorin本身具有有用的性质，也可以作为Caraporporrins的前体。此外，将使用碱催化的MacDonald[2+2]-方法来研究adj-二碳卟啉的合成，并将尝试制备三和四碳卟啉体系。我们将研究这组新的大循环的性质。