The recent progress in the ability of amine catalysis to functionalize polyunsaturated carbonyl compounds was made possible by highest occupied molecular orbital (HOMO)-raising or lowest unoccupied molecular orbital (LUMO)-lowering activations. In this context, the HOMO-raising dienamine and trienamine activation strategy has been explored extensively for the functionalization of polyconjugated carbonyl compounds at remote positions. This concept was recently stretched further to tetraenamine catalysis, a new activation strategy for amine-catalyzed HOMO-activation. The concept of tetraenamine catalysis is quite modern and only a few examples of the asymmetric Diels–Alder reaction are known so far. In this chapter, we will discuss the very first breakthroughs in the direction of tetraenamine catalysis.