Marine ascidian metabolite perophoramidine has since its isolation in 2002 attracted the interest of several research groups. The complex polycyclic structure with vicinal quaternary carbon stereocenters and two amidine functionalities constitutes a formidable synthetic challenge. In this project a new synthetic approach to dehalogenated perophoramidine has been investigated. The vicinal quaternary carbon stereocenters were introduced via a samarium mediated reductive dialkylation, in which the stereochemistry was determined by the metal chelate that formed, as outlined below. Several of the steps suggested in the synthetic approach have been successfully evaluated. Future work is needed to assess the remaining steps of the suggested route to dehalogenated perophoramidine.