• asymmetric catalysis;
  • donor–acceptor systems;
  • hydrogen bonding;
  • organocatalysis;
  • terpenoids


Chiral hydrogen-bond donors have played a crucial role in the progress of asymmetric catalysis as an essential tool in modern organic synthesis. Among these donors, thioureas have been found to be one of the most powerful systems in organocatalytic approaches. Within the last three years, a new generation of bifunctional thiourea catalysts has emerged as an effective way to promote highly demanding chemical transformations, frequently with success rates that are intriguingly higher than with other traditional thioureas. This new class of organocatalysts incorporates a bulky, rigid, and chiral terpene skeleton as one of the thiourea substituents, thus providing an additional and effective rigidifying (entropic) effect on the electrophile activation profile of thioureas. Structural integrations, either with additional Lewis basic nucleophile-activating motifs or with amino groups for enamine catalysis, have enabled their implementation in a wide repertoire of stereocontrolled catalytic processes. This Review charts the development of these new catalysts, as well as their applications in a wide variety of reactions and reaction sequences, with the hope of encouraging further progress in the field of thiourea-catalyst discovery and of bringing attention to the countless possibilities that are opened up by the tremendous success of terpene-derived thiourea catalysts.