The chemical investigation of Heliotropium transalpinum var. transalpinum Vell. (Boraginaceae) led to the isolation of transalpinecine (1), a novel pyrrolizidine alkaloid, in addition to known alkaloids subulacine (1β-2β-epoxy-1α-hydroxymethyl-8α-pyrrolizidine) (2), and 1α-2α-epoxy-1β-hydroxymethyl-8α-pyrrolizidine (3). The structures of the isolated compounds were elucidated based on spectroscopic data and theoretical calculations. © 2009 Elsevier Ltd. All rights reserved.