Mechanistic Switch in Dual Gold Catalysis of Diynes: C(sp3)–H Activation through Bifurcation—Vinylidene versus Carbene Pathways

Abstract
The other side of the mountain: Changing the framework of diyne systems opens up new cyclization modes for dual gold catalysis. Instead of a 5‐endo cyclization and gold vinylidenes a 6‐endo cyclization gives rise to gold‐stabilized carbenes as key intermediates for selective CH insertions.