The total syntheses of the complex pyrrole-imidazole alkaloids (+/-)-massadine and (+/-)-massadine chloride is described using a carefully orchestrated sequence of manipulations on highly polar and structurally complex intermediates. Key to the completion of this synthetic endeavor was the exploration of a unique and chemoselective method to oxidize unprotected guanidines under aqueous conditions in air, This oxidation has been optimized and applied to a selection of spirocyclic guanidines of varying complexity. Additionally, the 3,7-epi analogues of these interesting natural products have been synthesized and fully characterized.