This chapter compiles the reports available on the preformed stoichiometric dienamines, 1-aminobuta-1,3-dienes and 2-aminobuta-1,3-dienes, in the literature. It emphasizes the various synthetic methods existing for these preformed dienamine intermediates and their application as electron-rich dienes in Diels–Alder reactions with various dienophiles. This chapter also includes a few metal-catalyzed methods for the preparation of some preformed dienamine intermediates. A few of the preformed dienamine species are even employed in the synthesis of pharmaceutically important compounds.