A full account of the total synthesis of 18-demethyl-19-hydroxy-N a -demethyl-N b -methylsuaveoline (1), the structure assigned to macrocaffrine isolated from Rauwolfia caffra, is presented. The key steps involved are an intramolecular cycloaddition reaction of the oxazole–olefin 10 and a subsequent dehydration that generated the pentacyclic pyridine derivative 14. The spectral data and specific rotation of synthetic 1 were dissimilar to those reported for a natural sample, leaving the structure of this R. caffra alkaloid undefined.