Gold-Catalyzed 1,2-Rearrangement on Benzene Triggered by a Transient Dearomative Claisen Rearrangement.

1,2-Migration on arenes represents a powerful transformation, because of its chemical skeleton and exit vector editing ability. However, the corresponding dearomative mediated 1,2-migration on arene was ignored for decades, despite tremendous effort being devoted to develop the dearomative reaction, which mainly capitalized on breaking the planarity for three-dimensional diversification. Here, we report on the gold-catalyzed 1,2-rearrangement on benzene by the transient dearomatization of high-resonance energy benzene. This functional transposition strategy enabled rapid access to several precursors of extended π-conjugated molecules, showcasing its potential applications in materials sciences.