Towards dual‐metal catalyzed hydroalkoxylation of alkynes

Poly (vinyl ethers) are compounds with great value in the coating industry due to exhib-iting properties such as high viscosity, soft adhesiveness, resistance to saponification and solubility in water and organic solvents. However, the main challenge in this field is the synthesis of vinyl ether monomers that can be synthetized by methodologies such as vinyl transfer, reduction of vinyl phosphate ether, isomerization, hydrogenation of acetylenic ethers, elimination, addition of alcohols to alkyne species etc. Nevertheless, the most successful strategy to access to vinyl ether deriv-atives is the addition of alcohols to alkynes catalyzed by transition metals such as molybdenum, tungsten, ruthenium, palladium, platinum, gold, silver, iridium and rhodium, where gold‐NHC catalysts have shown the best results in vinyl ether synthesis. Recently, the hydrophenoxylation reaction was found to proceed through a digold‐assisted process where the species that determine the rate of the reaction are PhO‐[Au(IPr)] and alkyne‐[Au(IPr)]. Later, the improvement of the hy-drophenoxylation reaction by using a mixed combination of Cu‐NHC and Au‐NHC catalysts was also reported. DFT studies confirmed a cost‐effective method for the hydrophenoxylation reaction and located the rate‐determining step, which turned out to be quite sensitive to the sterical hin-drance due to the NHC ligands.