Three Chilean barberries, Berberis actinacantha Mart. ex Schult., B . darwinii Hook and [ulbar|B. valdiviana Phil. (Berberidaceae), have yielded several new isoindolobenzazepine and protoberberine alkaloids. Novel isoindolobenzazepines are (±)-13-deoxychilenine ( a ), pictonamine ( 10 ), chileninone ( 12 ), (±)-chileniimi ( 18 ) and (±)-palmanine ( 19 ). Highly oxidized protoberberines of particular interest include (±)-O-methylprechilenine ( 6 ) and (±)-prepseudopalmanine ( 21 ), together with 13-methoxy-8-oxyberberine ( 8 ). Isoindolobenzazepine alkaloids arise biogenetically from the rearrangement of highly oxidized protoberberines.