(2R,5R)-(-)-trans-2,5-Dimethylpyrrolidine is an important chiral auxiliary compound with a pseudo C2 axis. it is a diastereoselective alkylation of ketone enamines. (2R,5R)-(-)-trans-2,5-Dimethylpyrrolidine is highly stereoselective addition reactions of the enamine of β-keto esters (vinylogous urethanes). It has been involved in radical reactions of unsaturated amides.