DFT rationalization of the mechanism and selectivity in a gold-catalyzed oxidative cyclization of diynones with alcohols.

The mechanism, regioselectivity, and chemoselectivity in a gold-catalyzed oxidative cyclization of diynones with alcohols to give furan-3-carboxylate derivatives were explored by density functional theory (DFT). The obtained results revealed that the first step of the global reaction involves a nucleophilic attack of a pyridine-N-oxide derivative on the catalyst-ligated diynone, forming a vinyl intermediate that can isomerize to an α,α'-dioxo gold carbene upon the cleavage of the N-O bond. In the second step, a nucleophilic addition is also completed via pyridine-N-oxide instead of an alcohol proposed in the experiment. In the following steps, the selective nucleophilic addition of alcohol, 1,2-alkynyl migration, five-membered cyclization, and protodeauration lead to the furan-based products with the regeneration of the gold catalyst. The unique features of regio- and chemoselectivity were investigated in detail by the global reactivity index (GRI) and distortion/interaction analyses. Apart from fully rationalizing the experimental data, the DFT results provide an important contribution to understanding, optimizing, and further developing the related types of organic transformations.