Dynamics of Cooperative Palladium/Copper Catalysis for Aerobic Oxidative Difunctionalization of 1,3-Dienes with Aniline and Disilane

Pd-catalyzed aerobic oxidative functionalization of olefins has emerged as a powerful tool for step- and atom-economical bond formation. Redox mediators, such as Cu, Fe, and Co salts, facilitate the aerobic reoxidation of the Pd catalysts, maintaining catalytic turnover. In the present study, we explored the dynamics of a [Pd]/[Cu] cocatalyst system for the aerobic oxidative difunctionalization of 1,3-dienes with anilines and disilanes. This system exhibits distinctive catalytic performance compared with those based on conventional metal-complex catalysis. During the catalytic reaction, nanoparticles (NPs) comprising 8 nm polymeric PdI2 species on a CuO species are formed. Mechanistic studies indicated that these polymeric PdI2 species are leached out during the reaction and form monomeric Pd species. Catalyst redox process between Pd and Cu species occurred on the catalyst surface, and the Cu species adjacent to the Pd species facilitate the aerobic oxidative aminosilylation of 1,3-dienes to afford multisubstituted alkenes.