The new isoquinoline alkaloid (−)-peshawarine (1) has been isolated from Hypecoum parviflorum Kar. & Kir. (Papaveraceae). Its synthesis in the racemic form from coptisine (6b) involves a novel approach to cyclic hemiacetals in which the key step is the transformation of the aldehyde (±)-aobamine (10b) into the hemiacetal 12b using ethyl chloroformate. (±)-Corydalisol (11b) and (±)-canadaline (10a) have also been synthesized for the first time. The absolute configuration of (−)-1 was determined by chemical correlation with (+)-rhoeagenine methiodide (20). The chirality of the alkaloid (+)-canadaline (10a) has also been established by analogy to (+)-corydalisol (11b). (−)-Peshawarine (1), (+)-canadaline (10a), (+)-corydalisol (11b), and aobamine (10b), as well as hypecorine (22) and hypecorinine (23), are members of a new group of isoquinoline alkaloids, the secoberbines. © 1978, All rights reserved.