Aspidodasycarpine and lonicerine are a pair of epimeric aspidophylline-type alkaloids bearing vicinal quaternary C7 and C16. The first and enantioselective total syntheses of these molecules are described here. A Ru-catalyzed asymmetric transfer hydrogenation established the first stereocenter. An Au-promoted Toste cyclization was exploited to assemble the bridged tetracyclic core and define the geometry of the exocyclic olefin; electron deficient (p-CF3C6H4)3P was a suitable ligand for this transformation. An aldol condensation followed by an intramolecular indole C3 alkylation constructed the adjacent quaternary C7 and C16 diastereoselectively, leading to a pentacyclic lactol as an advanced common intermediate for synthesizing both alkaloids. The proposed structure of lanciferine, a highly oxidized congener of aspidodasycarpine, was synthesized from the lactol by tuning the oxidation states of various carbons.

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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.

Auf DNA‐Fang: Durch Oxidation mit Natriumperiodat oder Bestrahlung entstehen aus Phenylseleniden wie 1 ortho‐Chinonmethid‐Intermediate, die Doppelstrang‐DNA vernetzen. Die Kristallstrukturanalyse eines Derivats von 1 zeigt eine verdrehte Biphenyl‐Einheit; diese Beobachtung könnte erklären, warum 1 effektiv mit dem DNA‐Rückgrat wechselwirkt.