Bifunctional NHC‐Catalyzed Remote Enantioselective Mannich‐type Reaction of 5‐(Chloromethyl)furfural via Trienolate Intermediates

N‐heterocyclic carbene (NHC)‐catalyzed enantioselective Mannich‐type reactions of the biomass‐derived platform compound 5‐(chloromethyl)furfural (CMF) with imines were developed. A series of high‐value‐added chiral amines were afforded in good to high yields with excellent regio‐ and enantioselectivities. The bifunctional NHC derived from ʟ‐pyroglutamic acid efficiently steered the remote addition of the trienolate intermediate to the imine in a highly stereocontrolled manner. This represents the first enantioselective reaction proceeding via an NHC‐bound trienolate intermediate. NHC‐catalyzed enantioselective Mannich‐type reactions of 5‐(chloromethyl)furfural (CMF), an important biomass‐derived platform chemical, with aldimines afford chiral amines in good yields with excellent regio‐ and enantioselectivities. The use of a bifunctional NHC bearing a free hydroxy group enabled the remote addition of the trienolate intermediate to the imine to occur in a highly stereocontrolled manner.