Trioxacarcins DC-45-A2, DC-45-A1, A, D, C7"-epi-C, and C have been synthesized through stereoselective strategies involving BF3.Et2O-catalyzed ketone epoxide opening and gold-catalyzed glycosylation reactions, and the full structural assignment of trioxacacin C was deciphered via the syntheses of both of its C7" epimers. The gathered knowledge sets the foundation for the design, synthesis, and biological evalution of analogues of these natural products as potential payloads for antibody drug conjugates and other delivery systems for targeted and personalized cancer chemotherapy.