In the present thesis it is shown how aminocatalysis may be used to solve some problems for synthetic organic chemists. Combination of aminocatalysis with the concept of vinylogy is the key concept for the enantioselective functionalization of remote positions of carbonyl compounds. In the first chapter, a bifunctional primary amine-thiourea catalyst that can combine H-bond-directing activation of the electrophile with the dienamine activation is used for an asymmetric vinylogous aldol reaction. It has been demonstrated that using a chiral secondary amine, the potential of organocascade catalysis can be expanded by including vinylogous reactivity, functionalizing exclusive γ and δ positions. In the last chapter, it has been developed an enantioselective radical conjugate addition of enones by trapping photochemically generated carbon-centered radicals using iminium ion activation.