RUI: Platinum-Catalyzed Selective Carbon-Hydrogen (C-H) Functionalization Reactions: Mechanism and Synthetic Utility

美国国家科学基金会化学部的化学催化项目正在支持东卡罗莱纳大学的霍寿泉教授和李玉民教授的研究，开发将碳-氢键转化为碳-碳键的催化反应。 通过交换这些键，随后的反应可以产生更复杂的分子，这些分子可以用作药物发现和材料科学的基石。霍博士和李博士正在与本科生和硕士生合作，通过实验室实验和理论计算，更深入地了解反应机理。霍博士扩大了他的创新1-2-3本科研究增强计划，以吸引更多的学生进行研究，并更有效地培养他们。该项目正在扩大来自代表性不足群体的学生的参与，并通过与东卡罗莱纳大学暑期科学和数学创业项目（SVSM）的合作吸引高中生。该项目还为学生培养更强大的国家科学人才队伍，并为东部卡罗莱纳地区的教育，经济和社会发展做出贡献。霍博士和李博士正在研究一种独特的铂催化碳氢（C-H）酰化反应，并将这种欠发达的反应推进为实用的合成方法。与其它金属催化的C-H酰化反应相比，该铂催化的反应不含氧化剂和其它添加剂，并且也不含不期望的脱羰基副反应。因此，正在研究将α-、β-和γ-酮酯官能团、二酮基团和各种其他酰基引入各种芳基-杂芳基醚中的有效方法，从而产生许多生物学和/或医学上令人感兴趣的结构单元。霍博士和李博士也正在研究这种铂催化反应的机制，使用实验和计算相结合的方法。实验研究揭示了控制反应活性和选择性的潜在因素，而密度泛函理论（DFT）和轻推弹性带（NEB）方法被用来定位反应的最低能量途径，并预测关键中间体和过渡态的结构和稳定性。DFT也被用于设计新的催化剂。这项研究正在推进有机金属化学的基础知识，同时为广泛的有机化学界提供有效的方法。此外，本科生、硕士研究生、高中生也都从事有机和有机金属化合物的合成和表征、计算建模、数据分析和研究成果的传播。该奖项反映了NSF的法定使命，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。

The Chemical Catalysis Program of the NSF Division of Chemistry is supporting the research of Professors Shouquan Huo and Yumin Li at East Carolina University developing catalytic reactions that convert a carbon-hydrogen bond into a carbon-carbon bond. By exchanging these bonds, subsequent reactions can produce more complex molecules that can be used as building blocks in drug discovery and materials science. Drs. Huo and Li are working with undergraduate and master's-level students to gain a deeper understanding of the reaction mechanisms by using both laboratory experiments and theoretical calculations. Dr. Huo expands his innovative 1-2-3 Undergraduate Research Enhancement Program to attract more students to research and to train them more effectively. This project is broadening the participation of students from underrepresented groups and engaging high school students through collaboration with the East Carolina University Summer Ventures in Science and Mathematics (SVSM) Program. The project is also preparing students for a stronger national scientific workforce and contributing to educational, economic, and societal development in the eastern Carolina region.Drs. Huo and Li are studying a unique platinum-catalyzed carbon-hydrogen (C-H) acylation reaction and advancing this underdeveloped reaction into a practical synthetic method. Compared to other metal-catalyzed C-H acylation reactions, this platinum-catalyzed reaction is free of oxidants and other additives, and also free of undesired decarbonylative side reactions. As such, efficient methods to introduce alhpa-, beta-, and gamma-keto ester functional groups, diketone groups, and various other acyl groups into a variety of aryl-heteroaryl ethers, are being studied, thereby creating many biologically and/or medicinally interesting building blocks. Drs. Huo and Li are also investigating the mechanism of this platinum-catalyzed reaction using a combined experimental and computational approach. Experimental studies are unveiling the underlying factors controlling the reactivity and selectivity of the reaction while density functional theory (DFT) and the nudged elastic band (NEB) methods are being used to locate the lowest energy pathway of the reaction and predict the structures and stabilities of key intermediates and transition states. DFT is also being employed in the design of new catalysts. This research is advancing fundamental knowledge in organometallic chemistry while providing efficient methods to a broad organic chemistry community. Further, undergraduate students, master's-level graduate students, and high school students are engaged in the synthesis and characterization of organic and organometallic compounds, computational modeling, data analysis, and dissemination of research results.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.