Application of a modified Polonovski reaction for serratinine (1) resulted in generation of serratezomine A (2) with a novel seco-serratinine-type skeleton recently isolated from the club moss Lycopodium serratum var. serratum. This biomimetic transformation supports a biogenetic pathway proposed for serratezomine A (2). The absolute stereochemistry of serratezomine A (2) was established by an induced exciton chirality and modified Mosher methods.