Gas-Phase Ambident Reactivity of Monohydrated Enolate Anions

Article abstract of DOI:10.1021/jo00048a035

The gas-phase reactions between a series of monohydrated enolate anions and unsaturated perfluorocarbon compounds have been studied using Fourrier transform ion cyclotron resonance (FT-ICR) mass spectrometry.The influence of selective solvation at the oxygen atom on the ambident reactivity of enolate anions in the gas phase is investigated through comparison of the observed product distributions with previously obtained data for the corresponding unsolvated anions.This analysis indicates that probably in order to make the nucleophilic addition reactions energetically accessible the water molecule is vaporized from the reaction complex prior to the addition reaction step.This evaporation of a water molecule from the reaction complex is considered to recover the intrinsic chemical reactivity of the enolate anions which is confirmed by the agreement between the observed amibident chemical behavior of the monohydrated and unsolvated enolate anions.