The Chemical Structure, Dynamics and Mechanisms Program supports the work of Professor Robert E. Gawley of the Chemistry Department at the University of Arkansas for the study of chiral organolithium compounds. This effort is organized into three aims: 1) mechanistic studies and development of the scope of a catalytic dynamic resolution (CDR), 2) measurement of the thermodynamic parameters for carbanion inversion of selected, synthetically important, organolithium compounds and testing of CDR in the new systems, and 3) evaluation of the range of electrophiles suitable for use in stoichiometric and catalytic dynamic resolutions, specifically metal electrophiles for cross-coupling reactions. This project includes a collaborative effort with Dr. Iain Coldham at the University of Sheffield, U.K. Graduate students from the Gawley group will travel internationally to participate in the effort.
Control of stereoselectivity, the preferential formation of one mirror image of a chiral molecule, is one of the most important challenges facing synthetic chemists today. It is critical to the pharmaceutical industry, since most drugs are chiral and often only one of the forms is medically beneficial. This research develops new methods of stereoselective synthesis. The approach uses the electrophilic (electron-loving) substitution of chiral organometallic compounds, where a metal such as lithium, magnesium, copper or zinc is bound to an anionic (negatively charged) moiety. By careful analysis of the reactivity and structure of selected systems, the group is establishing principles of catalytic dynamic resolution to produce one chiral product selectively. The research involves an international collaboration with faculty and students in the United Kingdom and promotes learning through direct research experiences for undergraduate and graduate students.
