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A total synthesis of the mitochondrial complex I inhibitor piericidin A1 is described. It features a unique strategy for the key disconnection, highlighting a modified Negishi carboalumination/Ni-catalyzed cross-coupling on a polyenyne precursor.

Total Synthesis of Piericidin A1. Application of a Modified Negishi Carboalumination-Nickel-Catalyzed Cross-Coupling