CAS: Oxidation in Fragment Coupling and Fragmentation

CAS：片段偶联和断裂中的氧化

• 批准号: 2102626
• 负责人: Marisa Kozlowski
• 金额: $ 50万
• 依托单位: University of Pennsylvania
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-08-01 至 2024-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2102626&HistoricalAwards=false
• 关键词: CAS; Oxidation; Fragment; Coupling; Fragmentation

With the support of the Chemical Synthesis Program in the Division of Chemistry, Professor Kozlowski of the University of Pennsylvania is developing novel methods to forge new carbon-carbon bonds, the currency of organic chemistry, and to convert polymer waste products into value-added materials. These activities are helping to improve synthetic technology towards the more efficient and sustainable assembly of new materials, optimize heterogeneous catalysts for selective reactions, and find productive uses for polymer waste streams. The link between these projects is that the types of reactions being studied are oxidations, which reduce the number of carbon-hydrogen bonds in a molecule and replace them with carbon-carbon or carbon-oxygen bonds. This research program is also creating expanded access to chemistry instruction through the design of at-home organic chemistry experiments using non-toxic materials and Professor Kozlowski is actively involved in developing professional support systems for increasing diversity in STEM disciplines.The development of novel oxidative synthetic methods are important contributions to the goal of designing environmentally benign chemical processes. Professor Kozlowski and her research team are investigating new oxidative methods for complex molecule synthesis by optimizing oxidative phenol couplings for the preparation of polyaromatic hydrocarbons and studying heterogeneous catalysts for alkylarene cross coupling. Additional efforts are focused on developing new biomimetic pathways for the valorization of chemical waste with the photocatalytic use of oxygen. These studies are contributing to the goal of designing sustainable methods by: 1) engineering reactions at non-functionalized centers, thereby eliminating the need for complex pre-functionalized starting materials, 2) using oxygen as the terminal oxidizing agent, 3) using less toxic and less expensive base metals, and 4) converting waste materials to useful chemicals. The compounds being generated in these studies are also needed in the pharmaceutical, chemical, materials science, and agricultural industries as well as in basic biological and chemical research endeavors. Through these activities, Professor Kozlowski and her research team are working at the interface of organic, computational, and materials chemistry, which provides interdisciplinary training for a diverse group of postdoctoral researchers, graduate, and undergraduate students.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.

在化学系化学合成计划的支持下，宾夕法尼亚大学的Kozlowski教授正在开发新的方法来建立新的碳-碳键，有机化学的货币，并将聚合物废料转化为增值材料。这些活动有助于改进合成技术，以实现更有效和可持续的新材料组装，优化选择性反应的多相催化剂，并为聚合物废物流找到生产用途。这些项目之间的联系是，正在研究的反应类型是氧化反应，它减少了分子中的碳氢键的数量，并用碳碳或碳氧键取代它们。该研究计划还通过使用无毒材料设计家庭有机化学实验来扩大化学教学的机会，Kozlowski教授积极参与开发专业支持系统，以增加STEM学科的多样性。新型氧化合成方法的开发对设计环境友好的化学过程的目标做出了重要贡献。Kozlowski教授和她的研究团队正在研究复杂分子合成的新氧化方法，通过优化用于制备多环芳烃的氧化苯酚偶联和研究用于烷基芳烃交叉偶联的非均相催化剂。更多的努力集中在开发新的仿生途径，利用光催化利用氧气来稳定化学废物的价值。这些研究有助于通过以下方式实现设计可持续方法的目标：1）在非官能化中心进行工程反应，从而消除对复杂的预官能化起始材料的需求，2）使用氧气作为末端氧化剂，3）使用毒性较小且价格较低的贱金属，以及4）将废料转化为有用的化学品。在这些研究中产生的化合物也需要在制药，化学，材料科学和农业工业以及基础生物和化学研究工作。通过这些活动，Kozlowski教授和她的研究团队致力于有机化学、计算化学和材料化学的结合，为博士后研究人员、研究生和本科生提供跨学科的培训。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

Edge‐Decorated Polycyclic Aromatic Hydrocarbons by an Oxidative Coupling Approach

Edge——通过氧化偶联方法修饰多环芳烃

• DOI: 10.1002/chem.202203405
• 发表时间: 2022
• 期刊: Chemistry – A European Journal
• 作者: Gilmartin, Philip;Vu, Cassandra;Rotella, Madeline;Kaur, Jasjit;Kozlowski, Marisa
• 通讯作者: Kozlowski, Marisa

OH Roaming and Beyond in the Unimolecular Decay of the Methyl-Ethyl-Substituted Criegee Intermediate: Observations and Predictions

甲基乙基取代的 Criegee 中间体的单分子衰变中的 OH 漫游和超越：观察和预测

• DOI: 10.1021/jacs.3c07126
• 发表时间: 2023
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Liu, Tianlin;Elliott, Sarah N.;Zou, Meijun;Vansco, Michael F.;Sojdak, Christopher A.;Markus, Charles R.;Almeida, Raybel;Au, Kendrew;Sheps, Leonid;Osborn, David L.
• 通讯作者: Osborn, David L.

HAT Catalysts to Facilitate Acid Mediated Cleavage of Biaryl C-C Bonds in Binaphthols.

• DOI: 10.1021/acs.orglett.2c03325
• 发表时间: 2022-11-18
• 期刊: ORGANIC LETTERS
• 影响因子: 5.2
• 作者: Sojdak, Christopher A.;Kozlowski, Marisa C.
• 通讯作者: Kozlowski, Marisa C.

Substituent Effects on the Electronic Spectroscopy of Four-Carbon Criegee Intermediates

• DOI: 10.1021/acs.jpca.2c05502
• 发表时间: 2022-09-15
• 期刊: JOURNAL OF PHYSICAL CHEMISTRY A
• 影响因子: 2.9
• 作者: Liu, Tianlin;Zou, Meijun;Lester, Marsha I.
• 通讯作者: Lester, Marsha I.

Electronic Spectroscopy and Dissociation Dynamics of Vinyl-Substituted Criegee Intermediates: 2-Butenal Oxide and Comparison with Methyl Vinyl Ketone Oxide and Methacrolein Oxide Isomers

乙烯基取代的 Criegee 中间体：2-丁烯醛的电子光谱和解离动力学以及与甲基乙烯基酮氧化物和甲基丙烯醛氧化物异构体的比较

• DOI: 10.1021/acs.jpca.2c08025
• 发表时间: 2023
• 期刊: The Journal of Physical Chemistry A
• 作者: Wang, Guanghan;Liu, Tianlin;Zou, Meijun;Sojdak, Christopher A.;Kozlowski, Marisa C.;Karsili, Tolga N.;Lester, Marsha I.
• 通讯作者: Lester, Marsha I.