RUI: Aromaticity, Tautomerization and Metalation of Carbaporphyrinoid Systems

RUI：碳卟啉系统的芳香性、互变异构和金属化

• 批准号: 1855240
• 负责人: Timothy Lash
• 金额: $ 34万
• 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: 2019
• 资助国家: 美国
• 起止时间: 2019-09-01 至 2023-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1855240&HistoricalAwards=false
• 关键词: RUI; Aromaticity; Tautomerization; Metalation; Carbaporphyrinoid

With this award, the Chemical Synthesis program of the NSF Division of Chemistry is supporting the research of Professor Timothy Lash at Illinois State University to explore the synthesis, characterization, and reactivity of compounds that resemble a class of molecules called "porphyrins". Porphyrins possess many valuable properties and have applications in material science, catalysis and medicine. They also have an impressive array of functions in nature that range from oxygen transportation to photosynthesis. Porphyrins contain 4 nitrogen atoms, and related systems, called carbaporphyrins, have a carbon atom in place of one of the nitrogens. These molecules often have properties that complement those of naturally occurring porphyrins. The supported work is leading to efficient routes to novel carbaporphyrins and related systems that have unique reactivity and spectroscopic properties. Access to new classes of porphyrin analogues are improving our understanding of fundamental chemistry concepts such as aromaticity, a fundamental concept in chemistry which can lead to the enhanced stability of molecules. Furthermore, these types of structures commonly form stable complexes with palladium, rhodium and other important metal catalysts. Professor Lash and his students are studying applications of these molecules in the preparation of fine chemicals, as these derivatives modify the catalytic activity of bound metals. In addition, related compounds are being explored for use as photosensitizers in photodynamic therapy. These projects are not only providing an excellent environment for training undergraduates and Master's level graduate students in the field of organic synthesis, they are also exposing these students to the multidisciplinary nature of modern scientific research.In this research, synthetic routes to new porphyrin-like systems, including phenaliporphyrins, quiniporphyrins and carbachlorins, are being developed. Further application of the "3 + 1" variant of the MacDonald reaction is providing structures that incorporate phenalene, quinoline and numerous related heterocyclic units. The competition between aromatic hydroxyporphyrinoids and nonaromatic keto-tautomers can be particularly insightful, and these processes are being probed using spectroscopic techniques. True chlorins are widely studied, in part because they show the potential for applications as photosensitizers. Carbachlorins, which contain a carbocyclic ring in place of one of the pyrrole units, are generally more stable than the parent tetrapyrrolic structures and may have equally useful properties. However, carbachlorins have been little studied to date, and the development of new routes to these dihydroporphyrinoids will be of significant value. The introduction of fused aromatic rings onto carbaporphyrin structures offers the opportunity to further modify the properties of these compounds, and a new methodology to prepare carbaporphyrins with fused naphthalene, anthracene and related structural units is being developed. This approach is also being applied to be synthesis of larger dimeric systems that are expected to exhibit strong electronic interactions upon protonation. Hence, these investigations are revealing important new porphyrinoid systems and will have a major impact in the field of Porphyrin Chemistry.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

凭借该奖项，美国国家科学基金会化学部的化学合成项目正在支持伊利诺伊州立大学 Timothy Lash 教授的研究，探索类似于“卟啉”一类分子的化合物的合成、表征和反应性。卟啉具有许多有价值的特性，在材料科学、催化和医学方面有应用。它们在自然界中还具有一系列令人印象深刻的功能，从氧气运输到光合作用。卟啉含有 4 个氮原子，相关系统称为碳卟啉，用一个碳原子代替其中一个氮原子。这些分子通常具有与天然卟啉互补的特性。所支持的工作正在为新型碳卟啉和具有独特反应性和光谱特性的相关系统提供有效的途径。获得新类别的卟啉类似物正在提高我们对基本化学概念的理解，例如芳香性，这是化学中的一个基本概念，可以增强分子的稳定性。此外，这些类型的结构通常与钯、铑和其他重要金属催化剂形成稳定的配合物。拉什教授和他的学生正在研究这些分子在精细化学品制备中的应用，因为这些衍生物改变了结合金属的催化活性。此外，相关化合物正在探索用作光动力疗法中的光敏剂。这些项目不仅为有机合成领域的本科生和硕士研究生的培养提供了良好的环境，还让这些学生接触到现代科学研究的多学科性质。在这项研究中，正在开发新的类卟啉系统的合成路线，包括苯卟啉、喹啉卟啉和卡巴氯林。麦克唐纳反应“3+1”变体的进一步应用是提供包含苯酚、喹啉和许多相关杂环单元的结构。芳香族羟基卟啉类化合物和非芳香族酮互变异构体之间的竞争尤其具有洞察力，并且正在使用光谱技术来探索这些过程。真正的二氢卟酚被广泛研究，部分原因是它们显示出作为光敏剂的应用潜力。碳二氢化合物含有碳环代替吡咯单元之一，通常比母体四吡咯结构更稳定，并且可以具有同样有用的特性。然而，迄今为止，卡巴氯林的研究还很少，开发这些二氢卟啉类化合物的新路线将具有重要价值。在碳卟啉结构上引入稠合芳环为进一步改变这些化合物的性质提供了机会，并且正在开发一种用稠合萘、蒽和相关结构单元制备碳卟啉的新方法。这种方法也被应用于合成更大的二聚体系统，这些系统预计在质子化时表现出强的电子相互作用。因此，这些研究揭示了重要的新卟啉系统，并将对卟啉化学领域产生重大影响。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Exploring the limitations of the MacDonald ‘3 + 1’ condensation in the preparation of porphyrins with fused electron-withdrawing heterocyclic rings: Synthesis of a bis(thiadiazolo)benzoporphyrin and a related benzocarbaporphyrin

探索麦克唐纳-3-1-缩合在制备具有稠合吸电子杂环的卟啉中的局限性：双(噻二唑并)苯并卟啉和相关苯并碳卟啉的合成

• DOI: 10.1016/j.tetlet.2020.152576
• 发表时间: 2020
• 期刊: Tetrahedron Letters
• 影响因子: 1.8
• 作者: Cillo, Catherine M.;Geiger, Mark A.;Lash, Timothy D.
• 通讯作者: Lash, Timothy D.

Azulichlorins and Benzocarbachlorins Derived Therefrom

天青二氯林和由其衍生的苯并卡巴二氯林

• DOI: 10.1021/acs.joc.9b01578
• 发表时间: 2019
• 期刊: The Journal of Organic Chemistry
• 作者: Noboa, Mario A.;AbuSalim, Deyaa I.;Lash, Timothy D.
• 通讯作者: Lash, Timothy D.

Tetrabutyldideazaporphyrin

四丁基二脱氮杂卟啉

• DOI: 10.1016/j.tetlet.2020.152619
• 发表时间: 2020
• 期刊: Tetrahedron Letters
• 影响因子: 1.8
• 作者: Laxner, Jonathan T.;Lash, Timothy D.
• 通讯作者: Lash, Timothy D.

Telluracarbaporphyrins and a Related Palladium(II) Complex: Evidence for Hypervalent Interactions

• DOI: 10.1021/acs.inorgchem.1c01039
• 发表时间: 2021-06-17
• 期刊: INORGANIC CHEMISTRY
• 影响因子: 4.6
• 作者: Lash, Timothy D.;AbuSalim, Deyaa, I;Ferrence, Gregory M.
• 通讯作者: Ferrence, Gregory M.

Modified porphyrin chromophores: Synthesis and spectroscopic properties of nitronaphtho[1,2-b]porphyrins, benzothieno[2,3-b]porphyrins and their metalated derivatives

修饰卟啉发色团：硝基萘并[1,2-b]卟啉、苯并噻吩并[2,3-b]卟啉及其金属化衍生物的合成和光谱性质

• DOI: 10.1016/j.tet.2023.133601
• 发表时间: 2023
• 期刊: Tetrahedron
• 影响因子: 2.1
• 作者: Lash, Timothy D.;Wijesinghe, Chaminda B.;Manley, Jerad M.;Park, Stephanie M.
• 通讯作者: Park, Stephanie M.