The Organic Dynamics Program in the Chemistry Division will support Professor Richard D. Gandour's study of "Models to Test Proximity and Position in Catalysis" in the Chemistry Department at Louisiana State University, Baton Rouge. This project will use biarylethynyl model compounds to test ideas concerning how the placement and orientation of a catalytic functional group affect the rate at which it serves to accelerate a reaction. This project in intramolecular recognition will investigate the general base catalyzed hydrolysis of a series of esters in order to determine how critical to rate enhancement is the positioning (distance and orientation) of the catalytic group and the substrate in an enzymatic active site. The models being studied have been selected so that comparisons are made between systems differing only in the number of degrees of rotational freedom and/or the time-average distance between reacting groups. The rate enhancements engendered by proximity are being determined by comparing the hydrolysis rates of compounds with free rotation (no tether) with those containing tethers of varying lengths.
