Enantioselective Reactions Catalyzed by N‐Heterocyclic Carbenes

Enantioselective organocatalysis by using N‐heterocyclic carbenes (NHCs) has emerged as a powerful strategy for the construction of complex chiral molecules. Recently, remarkable advances have been made in enantioselective NHC‐catalyzed reactions that involve diverse activation intermediates, such as Breslow intermediates, homoenolate intermediates, α,β‐unsaturated acylazoliums, azolium enolates, and azolium dienolates, which are generated by the nucleophilic addition of NHCs to aldehydes. Furthermore, NHC‐catalyzed reactions that proceed through non‐covalent bonding interactions have also been developed. Carbenes mean Heinz: The use of N‐heterocyclic carbenes (NHCs) as catalysts has emerged as one of the most‐powerful strategies for the construction of complex molecules. Recent advances in enantioselective NHC‐catalyzed reactions that have been published since 2012 are highlighted and discussed.