Many active compounds contain pyrrole thione structure which has some applicability in the biological field.We studied that isothiocyanates and substituted methylene malononitrile reacted bifunctional organocatalysts as a catalysts, and synthesized some new chiral pyrrole thione structure compounds.These compounds contained two chiral centers, and between of similar polar one-pare diastereoisomers were very hard separated by column chromatography on silica gel.To the best knowledge of us, the separation of these compounds has not been reported yet.