Recent advances in asymmetric organocatalysis mediated by bifunctional amine-thioureas bearing multiple hydrogen-bonding donors.

Organocatalysis has proven to be one of the most rapidly developing and competitive research areas in asymmetric catalysis since 2000, and has become a third branch besides biocatalysis and transition metal catalysis. In this feature article, recent progress from our research group on asymmetric organocatalysis, focusing on fine-tunable amine-thiourea catalysis, is described. Design of novel bifunctional amine-thiourea organocatalysts based upon the synergistic activation strategy via multiple hydrogen bonds and their applications in asymmetric C-C, C-N, and C-S bond-forming reactions under mild conditions are discussed in detail. The most attractive feature of the newly designed fine-tunable amine-thiourea catalysts is the incorporation of multiple hydrogen bonding donors and stereogenic centers.