Selective Catalytic [3+n]-Cycloaddition Reactions with Vinyldiazo Compounds

通过这一奖项，化学系的化学催化计划正在支持德克萨斯大学圣安东尼奥分校的迈克尔·P·道尔教授的研究。多伊尔教授正在开发一类被称为“环加成”的反应，这种反应形成了原子环。这些环是许多重要化合物的基础，包括生物活性分子、药物和材料的前体。多伊尔教授设计了能够控制产品三维形状的化学系统，这一特征对合成具有重要药用价值的分子至关重要。此外，其中一些环加成反应使用了富含稀土的金属来加速反应。该项目为化学科学领域的下一代多样化研究人员提供培训和准备。从事该项目的本科生和研究生在获得现代合成方法和实验室技术方面的专业知识的同时，暴露在一个具有智力刺激和挑战性的环境中，这将为他们未来在STEM领域的职业生涯做好准备。复杂手性分子的成本效益制备直接依赖于可持续合成方法的可用性。在这个项目中，Doyle教授正在推进催化(3+n)-环加成反应的发现和发展，其中n=1、2或3，用于合成碳环和杂环化合物。他和他的团队正在使用一种金属稳定的三碳乙烯基卡宾，这种化合物要么来自乙烯基重氮化合物，要么来自给体-受体环丙烷，以选择性地形成包含4至6元环和最多两个杂原子的产品。这些环加成反应中的立体选择性是通过手性配体来实现的，这些配体将反应物限制在乙烯基卡宾的一侧，提供了高达99：1的对映体比。使用稀土丰富的铜催化剂和使用环丙烯作为乙烯基卡宾的来源也得到了积极的探索。该奖项反映了NSF的法定使命，通过使用基金会的学术价值和更广泛的影响审查标准进行评估，被认为是值得支持的。

With this award, the Chemical Catalysis Program of the Division of Chemistry is supporting the research of Professor Michael P. Doyle of the University of Texas at San Antonio. Professor Doyle is developing a class of reactions known as "cycloadditions" that form rings of atoms. These rings are the building blocks of many important compounds, including precursors to biologically active molecules, pharmaceutical drugs, and materials. Professor Doyle has designed chemical systems that are capable of controlling the 3-dimensional shape of the products, a feature that is crucial to the synthesis of molecules of medicinal importance. In addition, some of the these cycloaddition reactions use earth-abundant metals to speed up the reaction. This project provides a training and preparation for the next generation of diverse researchers in the chemical sciences. Undergraduate and graduate students working on this project gain expertise in modern synthetic methods and laboratory techniques while being exposed to an intellectually stimulating and challenging environment that will prepare them for future careers in STEM fields.The cost-effective preparation of complex chiral molecules is directly dependent on the availability of sustainable synthetic methodologies. In this project, Professor Doyle is advancing the discovery and development of catalytic (3+n)-cycloaddition reactions where n=1, 2, or 3, for the synthesis of carbocyclic and heterocyclic compounds. He and his team are using a metal-stabilized three-carbon vinylcarbene that is derived either from a vinyldiazo compound, or a donor-acceptor cyclopropane, to selectively form products containing 4 to 6-membered rings and up to two heteroatoms. Stereoselectivity in these cycloaddition reactions is imparted via chiral ligands, which restrict the approach of a reactant to one side of the vinylcarbene, providing enantiomeric ratios as high as 99:1. The use of earth-abundant copper catalysts, and the use of cyclopropenes as vinylcarbene sources are also actively pursued. There is also a strong commitment to engaging a diverse group of students to carry out this research.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.