A new pyrrolidone-diene synthon was devised, and the inverse-electron-demand Diels-Alder reaction of pyrrolidone-dienes with enals catalyzed by chiral secondary amines has been disclosed. A variety of enantioenriched, multifunctionalized hexahydro-isoindol-1-one derivatives were obtained in good yields (up to 75%) with excellent stereoselectivities (up to > 20:1 dr and > 99% ee).