A highly efficient synthesis of alpha-alkylidene or benzylidene-beta-diketones from readily available propargylic esters has been developed. The proposed key transformation is a novel intramolecular acyl migration to nucleophilic AuIII-C(sp2) bonds. Noteworthy features of this method are its efficiency and stereoselectivity. The yields of this reaction were mostly close to quantitative, and high to excellent stereoselectivities were observed in the cases of dienyl beta-diketones.