Abstract The reaction mechanism of the gold‐catalyzed synthesis of functionalized acenes via cascade [3,3]‐oxo migration/[1,5]‐H shift is documented by DFT calculations. Interestingly, the overall reaction machinery displays a notable exothermic profile and the pivotal role played by the metal center in the initial [1,3]‐acyloxy migration of 1 was also discovered. Contrarily, contribution of the gold complex in the H shift was negligible as the energy profiles of the gold‐based and metal‐free protocols are very similar in the latest stage.
