Since the discovery of the in situ generation of 2-aminobuta-1,3-dienes by the Barbas group, these moieties have been incessantly utilized in different [4+2]-cycloadditions and cascade reactions. Barbas dienamines have performed well in homo- and hetero-[4+2]-cycloadditions. Recently they were utilized in a Michael reaction also. A summary of the diverse catalytic methods of preparing Barbas dienamines with the help of various primary and secondary amines and their applications in making interesting and highly functionalized frameworks, such as spiroketones, bridged bicyclic compounds, sulfamate-fused 2,6-disubstituted piperidin-4-ones, tetrahydropyranones, β-nitrocyclohexanecarboxylic esters, spirocyclic oxindoles, etc., are presented. Further, these Barbas dienamines have been employed in the total synthesis of some complex natural products, like nominine, and in a few pharmaceutically important molecules, proving their significance.