Pd-Catalyzed Regioselective Homobenzannulation of Enynals

Regio- and chemoselectivities in the synthesis of polysubstituted benzenes have posed a significant scientific obstacle for an extended period. Herein, we report a tunable Pd-catalyzed homobenzannulation of enynals, enabling divergent construction of 1,2,4-tri- and 1,4-disubstituted benzenes from identical substrates via unconventional selectivity. In particular, the interesting reaction model is verified by a variety of control experiments, offering theoretically valuable insight for the rational design of benzannulation reactions.