The Importance of Conformation of the Tetrahedral Intermediate in the Hydrolysis of Esters. Selective Cleavage of the Tetrahedral Intermediate Controlled by Orbital Orientation

Abstract

The hydrolysis or the transesterification of esters proceeds via a hemi-orthoester tetrahedral intermediate. There are nine different gauche conformers possible for such a tetrahedral intermediate and it is proposed that each of them should decompose in a highly selective manner. It is further proposed that the lone pair orbitals of the oxygen atoms control this selective decomposition.