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
基本信息
- 批准号:1855240
- 负责人:
- 金额:$ 34万
- 依托单位:
- 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:
- 关键词:
项目摘要
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.
有了这个奖项,NSF化学部的化学合成计划正在支持伊利诺伊州州立大学的Timothy Lash教授的研究,以探索类似于一类称为“卟啉”的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性质,在材料科学、催化和医学方面有应用。它们在自然界中也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,相关的系统称为碳卟啉,其中一个氮原子被一个碳原子取代。这些分子通常具有与天然卟啉互补的性质。支持的工作是导致有效的路线,以新颖的碳卟啉和相关系统,具有独特的反应性和光谱特性。获得新的卟啉类似物类别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,可以提高分子的稳定性。此外,这些类型的结构通常与钯、铑和其他重要的金属催化剂形成稳定的络合物。Lash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,也使这些学生接触到现代科学研究的多学科性质。在本研究中,正在开发新的卟啉类系统的合成路线,包括非那卟啉,喹啉和氨甲酰氯。麦克唐纳反应的“3 + 1”变体的进一步应用是提供并入非那烯、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可能特别有见地,这些过程正在使用光谱技术进行探测。真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。含有碳环代替吡咯单元之一的氨甲酰氯通常比母体四吡咯结构更稳定,并且可以具有同样有用的性质。然而,卡巴胆碱迄今为止研究甚少,开发新的路线,这些二氢卟啉类化合物将具有重要价值。在碳卟啉结构上引入稠合芳环为进一步修饰这些化合物的性质提供了机会,并且正在开发一种制备具有稠合萘、蒽和相关结构单元的碳卟啉的新方法。这种方法也被应用于合成更大的二聚体系统,预计质子化后表现出较强的电子相互作用。因此,这些研究揭示了重要的新类卟啉系统,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知识价值和更广泛的影响进行评估而被认为值得支持。审查标准。
项目成果
期刊论文数量(17)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
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:
- 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:
- 影响因子:0
- 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:
- 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:
- 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:
- 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.
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Timothy Lash其他文献
OBESITY IN YOUNG ADULT MEN AND RISK OF TYPE II DIABETES, CARDIOVASCULAR MORBIDITY, OR DEATH BEFORE 55 YEARS OF AGE: A DANISH 33-YEAR FOLLOW-UP STUDY
- DOI:
10.1016/s0735-1097(13)60032-7 - 发表时间:
2013-03-12 - 期刊:
- 影响因子:
- 作者:
Morten Schmidt;Sigrun A. Johannesdottir;Stanley Lemeshow;Timothy Lash;Sinna P. Ulrichsen;Hans Erik Boetker;Henrik Toft Soerensen - 通讯作者:
Henrik Toft Soerensen
Correction: Socioeconomic position and prognosis in premenopausal breast cancer: a population-based cohort study in Denmark
- DOI:
10.1186/s12916-023-02987-4 - 发表时间:
2023-08-17 - 期刊:
- 影响因子:8.300
- 作者:
Cathrine Fonnesbech Hjorth;Per Damkier;Bent Ejlertsen;Timothy Lash;Henrik Toft Sørensen;Deirdre Cronin-Fenton - 通讯作者:
Deirdre Cronin-Fenton
Timothy Lash的其他文献
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{{ truncateString('Timothy Lash', 18)}}的其他基金
RUI: New Porphyrinoid Architectures with Extended Conjugation Pathways
RUI:具有扩展共轭途径的新型卟啉结构
- 批准号:
2247214 - 财政年份:2023
- 资助金额:
$ 34万 - 项目类别:
Standard Grant
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 - 财政年份:2015
- 资助金额:
$ 34万 - 项目类别:
Standard Grant
RUI: Carbaporphyrins, Neo-Confused Porphyrins and Related Systems
RUI:碳卟啉、新混乱卟啉及相关系统
- 批准号:
1212691 - 财政年份:2012
- 资助金额:
$ 34万 - 项目类别:
Continuing Grant
Synthesis of Highly Modified Porphyrinoid Systems
高度修饰的卟啉系统的合成
- 批准号:
0911699 - 财政年份:2009
- 资助金额:
$ 34万 - 项目类别:
Standard Grant
Carbaporphyrins and other highly modified porphyrinoid systems
碳卟啉和其他高度修饰的类卟啉系统
- 批准号:
0616555 - 财政年份:2006
- 资助金额:
$ 34万 - 项目类别:
Standard Grant
Porphyrins, Carbaporphyrins and Related Conjugated Macrocycles
卟啉、碳卟啉和相关共轭大环化合物
- 批准号:
0134472 - 财政年份:2002
- 资助金额:
$ 34万 - 项目类别:
Standard Grant
Synthesis of Novel Porphyrinoids by the "3 + 1" Approach
“3 1”法合成新型卟啉类化合物
- 批准号:
9732054 - 财政年份:1998
- 资助金额:
$ 34万 - 项目类别:
Continuing Grant
Synthesis of Cycloalkanoporphyrins and Related Highly Conjugated Systems
环烷卟啉及相关高度共轭体系的合成
- 批准号:
9500630 - 财政年份:1995
- 资助金额:
$ 34万 - 项目类别:
Continuing Grant
Synthesis of Novel Porphyrins with Exocyclic Rings
新型环外卟啉的合成
- 批准号:
9201149 - 财政年份:1992
- 资助金额:
$ 34万 - 项目类别:
Continuing Grant
相似海外基金
Pyrrole-Modified Porphyrins: Platforms to Probe the Malleability of Porphyrinoid Conformation and Aromaticity
吡咯修饰的卟啉:探测类卟啉构象的延展性和芳香性的平台
- 批准号:
2400038 - 财政年份:2024
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CAS: Exploiting Pro-Aromaticity for Triplet Photochemistry: Synthesis, Aromaticity, & Photophysics
CAS:利用亲芳香性进行三线态光化学:合成、芳香性、
- 批准号:
2247930 - 财政年份:2023
- 资助金额:
$ 34万 - 项目类别:
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Synthesis and Properties of Aggregated Antiaromatic Molecules: Cyclobutadiene Dimers and Three-Dimensional Aromaticity
聚集抗芳香分子的合成和性质:环丁二烯二聚体和三维芳香性
- 批准号:
21K05023 - 财政年份:2021
- 资助金额:
$ 34万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
Post-nanocarbon synthetic chemistry by control of aromaticity
通过控制芳香性进行后纳米碳合成化学
- 批准号:
21H01931 - 财政年份:2021
- 资助金额:
$ 34万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
Exploiting the interface between aromaticity and non-aromaticity
利用芳香性和非芳香性之间的界面
- 批准号:
EP/T011599/1 - 财政年份:2020
- 资助金额:
$ 34万 - 项目类别:
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Organic synthesis by means of breaking aromaticity via reduction
通过还原破坏芳香性进行有机合成
- 批准号:
19H00895 - 财政年份:2019
- 资助金额:
$ 34万 - 项目类别:
Grant-in-Aid for Scientific Research (A)
Photophysics and conductivity of TTF-annulated porphyrinoids with excited-state aromaticity reversal
具有激发态芳香性逆转的 TTF 环卟啉类化合物的光物理和电导率
- 批准号:
19F19345 - 财政年份:2019
- 资助金额:
$ 34万 - 项目类别:
Grant-in-Aid for JSPS Fellows
Aromaticity: The Key to Higher Energy Density Organic Batteries
芳香度:更高能量密度有机电池的关键
- 批准号:
504290-2017 - 财政年份:2019
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Development of New Lewis Base Catalyst based on the Aromaticity of Cyclopropenones
基于环丙烯酮芳香性的新型路易斯碱催化剂的研制
- 批准号:
19K15569 - 财政年份:2019
- 资助金额:
$ 34万 - 项目类别:
Grant-in-Aid for Early-Career Scientists
Aromaticity: The Key to Higher Energy Density Organic Batteries
芳香度:更高能量密度有机电池的关键
- 批准号:
504290-2017 - 财政年份:2018
- 资助金额:
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