The Mechanism of Hydrolysis of Imidate Salts. The Importance of Stereoelectronic Control and p H of the Reaction Medium on the Cleavage of Tetrahedral Intermediates

Abstract

Hydrolysis of anti imidate salts give the ester amine products exclusively over the entire range of pH. Hydrolysis of syn imidate salts in acidic and neutral conditions give the ester amine products only; in basic conditions, mixtures of ester amine and amide alcohol products are observed. These results are explained by the application of the new theory of stereoelectronic control on the various ionic forms T + , T ± , and T − of the tetrahedral intermediate. For syn imidate salts, conformational changes of the tetrahedral intermediate must occur in order to have cleavage with stereoelectronic control.