Intramolecular participation by enolate anions in the cleavage of aryl esters of mesitoic acid; carbon–carbon bond formation in aqueous and alcoholic solvents

Abstract

The mechanistic criteria which determine whether nucleophilic participation by the acetyl group in the cleavage of aryl esters of mesitoic acid will occur through oxygen or carbon are discussed. Participation through oxygen, which must be preceded by formation of a tetrahedral adduct at the carbonyl group is replaced by participation through carbon even in hydroxylic solvents, when formation of the adduct is prevented in the esters 2-acetylphenyl mesitoate (I) and 1-acetyl-2-naphthyl mesitoate (IV).