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The enantioselective first total syntheses of marine pentacyclic indolosesquiterpenoids xiamycins D (4) and E (5) have been described for the first time to the best of our knowledge. The synthetic approach was designed to feature functionalization of enantiopure Wieland–Miescher ketone, Michael addition followed by Heck-type annulation/aromatization, regioselective sp3(C–H) activation, benzylic oxidation and diastereoselective reduction.

Graphical abstract: Enantioselective first total syntheses of the antiviral natural products xiamycins D and E

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