The one-pot three-component reaction of secondary α-amino acids with dialkyl acetylenedicarboxylate and N-substituted maleimides afforded functionalized pyrrolo[3,4-a]pyrrolizines, pyrrolo[3′,4′:3,4]pyrrolo[1,2-c]thiazoles, pyrrolo[3,4-a]indolizines and octahydropyrrolo[3,4-c]pyrroles.