Does Aromaticity in a Reaction Product Increase or Decrease the Intrinsic Barrier? Kinetics of the Reversible Deprotonation of Benzofuran-3(2H)-one and Benzothiophene-3(2H)-one

Claude F. Bernasconi, and Moisés Pérez-Lorenzo
J. Am. Chem. Soc., 2007, 129, 2704–2712


A kinetic study of the reversible deprotonation of benzofuran-3(2H)-one (3H-O) and benzothiophene-3(2H)-one (3H-S) by amines and hydroxide ion in water at 25 °C is reported. The respective conjugate bases, 3–O and 3–S, represent benzofuran and benzothiophene derivatives, respectively, and thus are aromatic. The main question addressed in this paper is whether this aromaticity has the effect of enhancing or lowering intrinsic barriers to proton transfer. These intrinsic barriers were either determined from Brønsted plots for the reactions with amines or calculated on the basis of the Marcus equation for the reaction with OH-; they were found to be lower for the more highly aromatic benzothiophene derivative, indicating that aromaticity lowers the intrinsic barrier. It is shown that the reduction in the intrinsic barrier is not an artifact of other factors such as inductive, steric, resonance, polarizability, and π-donor effects, although these factors affect the intrinsic barriers in a major way. Our results imply that aromatic stabilization of the transition state is ahead of proton transfer; this contrasts with simple resonance effects, which typically lag behind proton transfer at the transition state, thereby increasing intrinsic barriers.