Primary kinetic isotope effects in hydride transfer: experimental studies of intramolecular hydride migration and ab initio molecular orbital calculations of model systems

Abstract

Measurements of the primary kinetic hydrogen isotope effects for the intramolecular migration of hydride accompanying the rearrangements of (i) hydroxy-ketones involving 1,4-migration of hydride between ketonic carbonyl groups and (ii) phenylglyoxal hydrates to their corresponding mandelic acids are described. The results are discussed using ab initio MO calculations of model systems, with a variety of basis sets. The value of such model calculations is demonstrated.