Three Chilean barberries, Berberisactinacantha Mart. ex Schult., B. darwinii Hook and [ulbar|B. valdivianaPhil. (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. © 1984.