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

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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.