Density functional theory (DFT) calculations reveal a distinct mechanism for the Au(I)-catalyzed synthesis of bicyclo-[2.2.1]heptanes through cycloisomerizations of 3-alkoxyl-1,6-diynes. The proposed mechanism highlights the crucial involvement of an allyl-gold species and rationalizes all experimental observations, including the solvent-controlled chemodivergence of the reaction. Specifically, in the less polar toluene solvent, the reaction involves a key allyl-gold species with an energy barrier of 24.1 kcal mol-1, leading to the bridged ring product. Conversely, in the polar 1,2-dichloroethane solvent, the reaction occurs via an alkyl-gold species with an energy barrier of 29.2 kcal mol-1, delivering the monocyclic product. This new reactivity concept could potentially assist the exploration of new and unconventional strategies for the preparation of bridged ring systems.

You have access to this article

Please wait while we load your content... Something went wrong. Try again?