In this project ("The Kinetics of Isomer-Specific Oxygen Exchange Reactions of Optically Active Alcohols as a Function of Acid-Catalyzed Racemization") in the Organic Dynamics Program of the Chemistry Division, Professor Margaret V. Merritt of the Chemistry Department at Wellesley College will determine the rate constants for oxygen exchange for isomers as a function of racemization of a series of chiral alcohols. These detailed kinetic studies will enhance the understanding of reaction mechanisms and reaction intermediates in these and related systems. The rate constants for oxygen exchange as a function of racemization of a series of chiral alcohols will be used to probe the structural features that lead to asymmetric solvation of carbocation intermediates and to investigate the structure of water within the solvation sphere. The mechanistic conclusions will be based on the microscopic rate constants for three competing processes at the alpha carbon atom and the oxygen isotope effects for these processes. The three competing processes being studied are substitution (O-18 exchange) without inversion, substitution (O-18 exchange) with retention, and inversion without substitution.
