The examination of the alkaloids present in Ceratocapnos heterocarpa (Papaveraceae) had led to the isolation of the new protoberberine alkaloid, (-)-malacitanine. Characteristic structural features for this alkaloid are the 1,2,10,11-substitution pattern and the hydroxymethyl group at C-8. The synthesis of (.+-.)-malacitanine and its C-8 epimer from the benzylisoquinoline (.+-.)-norcrassifoline has been developed. Spectroscopic data (pmr, cmr and ir) for several C-8 substituted protoberberine alkaloids are reported in connection with the quinolizidine conformation.