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

The basic hydrolysis of N-disubstituted imidate salts proceeds via a hemi-orthoamide tetrahedral intermediate which can in principle give amide–alcohol or ester–amine products. Experimental evidence has been obtained which shows that the specific conformation of the tetrahedral intermediate determines products formation and it is further suggested that the orientation of the lone pair orbitals of the heteroatoms governs this remarkable selective decomposition.