Unveiling the Reaction Machinery of the [AuI]-Catalyzed Synthesis of Substituted Acenes by a [1,5]-H Shift Cascade Reaction

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.