The Chemical Structure, Dynamics and Mechanisms Program of the Chemistry Division supports Professor Matthew Meyer at the University of California, Merced for studies into the origins of stereoselection in asymmetric reductions and hydrogenations. Kinetic isotope effects will be used (KIEs) to quantitatively probe physical interactions that govern stereoselection in Corey-Bakshi-Shibata reductions and in Ru(II) catalyzed hydrogenations. The KIEs will be used to develop experimentally-corroborated transition structure models of highly stereoselective hydrogenations. A new method, isotopic perturbation of stereoselection, will be used to study systematic changes in Ru(II) catalyst environment using the series of TunePhos ligands. The transition structures for the reactions studied will be investigated computationally in order to interrogate the interactions that govern stereoselection.
Catalytic asymmetric reactions are of great importance to the fine chemicals and pharmaceutical industry. These industries, with their current focus on reducing feedstocks and enabling environmentally friendly technologies, have a critical need for new catalytic asymmetric methodologies. Surprisingly, the detailed mechanisms by which chirality is transferred are poorly understood in most developing methodologies. This project will refine the mechanistic understanding of stereoselection in two broad classes of reactions. Young scientists must be stewarded as they develop into professionals. The project will provide training to a diverse group of students, many from under-represented groups. An important component will involve exposing undergraduates to computational chemistry as well as the experimental aspects of organic chemistry. The PI will also be involved in outreach activities with Merced County 4-H that include the National Science Day 4-H experiment.
