In the last two decades, enantioselective organocatalysis has established itself as one of the three pillars of asymmetric catalysis. The rapid growth in the area is due to the rationalization of organocatalysis based on the generic modes of catalyst activation, being applied to several types of reactions, in a rather generic and predictable way and providing high enantioselectivities. This tutorial review presents the evolution of this area through a brief discussion on all generic modes of activation previously systematized in the literature: activation via enamine, iminium ion, hydrogen-bonding, counterion, SOMO, photoredox, carbene and phase-transfer, and the recent advances in the area.

Successful Heck-Matsuda arylations of non-activated olefins applying microwave irradiation as an alternative heating mode are presented. Cleaner reactions were performed with arenediazonium tetrafluoroborates bearing electron-donating and electron-withdrawing groups in good to excellent yields with reaction times reduced from 3.5-18 h to 12-30 min.