Total Synthesis of Aquayamycin

An efficient and practical total synthesis of aquayamycin has been accomplished. The highly oxidized and stereochemically complex tetracyclic ring system was constructed using three key reactions: 1) highly diastereoselective 1,2‐addition of C‐glycosyl naphthyllithium to a cyclic ketone, 2) indium‐mediated site‐selective allylation‐rearrangement sequence of naphthoquinone, and 3) diastereoselective intramolecular pinacol coupling. This synthetic strategy offers a novel and efficient pathway to prepare aquayamycin‐type angucycline antibiotics. Efficient and practical total synthesis of aquayamycin has been accomplished. The complex tetracyclic ring system was constructed by highly diastereoselective 1,2‐addition, indium‐mediated site‐selective allylation‐rearrangement, and diastereoselective intramolecular pinacol coupling.