Gold-Catalyzed Interrupted Relay Heck Reaction

Herein, we disclose the gold-catalyzed interrupted relay Heck reaction successfully demonstrating the implementation of a chain-walking process for the first time in a catalytic fashion. The reaction involves the merging of three distinct reactivities such as the Heck reaction, chain-walking, and anti-addition via π-activation to provide direct access to tetrahydronaphthalenes and octahydrophenanthrenes with high diastereoselectivity. We have also demonstrated the application of the interrupted chain-walking reaction in the development of 1,3-diarylation and 1,n-hydroarylation (n = 3, 4) of alkenes.