The Addition of Carbanions to the Carbonyl Group in the Gas Phase

Article abstract of DOI:10.1021/ja00396a006

The reaction of a variety of carbanions with esters in the gas phase proceeds by an addition-elimination-deprotonation mechanism, similar to that for the Claisen condensation in solution.The observed ion-molecule reactivities are analyzed in terms of a triple-minimum reaction coordinate.The thermochemistry of the various barriers along this coordinate explains the occurrence or absence of the condensation product.The effect of solvation on the reaction coordinate and the nature of the reactants is discussed.