We focused on the asymmetric organocatalysis, making major achievements on the N-heterocyclic carbenes (NHCs)-catalyzed stereoselective reactions for the synthesis of heterocyclic compounds. Heterocycles present wildly in various bioactivie compounds, pharmaceuticals and pesticides. After synthesis of several series of novel NHCs based on L-pyrogultamic acid, we successfully developed: NHC-catalyzed cyclization reactions of ketenes; Chiral NHC and cinchona alkaloids-catalyzed cyclization of α,β-unsaturated acyl chlorides;  NHCs-catalyzed cascade reactions of aldehydes;  NHC-catalyzed reactions of C-C unsaturated bonds. Those works give the new directions of NHC-catalyzed reactions, and have strong potential applications in synthesis of multisubstituted heterocycles and their derivatives.