Abstract
The different theories that account for the stereochemical characteristics of the deamination of aliphatic and alicyclic amines compared to solvolysis of the corresponding sulphonates and halides are examined. There is a discussion on the recent hypothesis concerning the relative increase of electron demand for the participation of neighbouring groups and bonds in deamination compared to solvolysis, making it possible to predict the direction of skeletal rearrangements in reactions involving elimination of nitrogen and to carry out deliberately such rearrangements when they do not occur in reactions with classical leaving groups. Questions concerning the applicability of the extended Hammond postulate and the Curtin–Hammett principle to reactions that involve decomposition of alkyldiazonium ions are discussed.
The bibliography includes 73 references.