The PhD dissertation relied on the development of new, operationally simple synthetic reactions using aminocatalysis, photochemistry and their combination. Asymmetric aminocatalysis has allowed to develop the elusive catalytic asymmetric Diels-Alder reaction of in situ generated ortho-quinodimethane intermediates. Further studies on the indole-2,3-quinodimethane strategy allowed the development of a multicatalytic one-pot Diels-Alder/benzoin reaction sequence and an asymmetric aza-Michael reaction. In a six months research period in Princeton, the direct β-aldol reaction has been achieved via the synergistic combination of photoredox catalysis and organocatalysis. Finally, an operationally simple protocol for the direct aromatic perfluoroalkylation of α-cyano arylacetates has been developed using visible light-EDA complex activation.