Mechanistic Studies of Gold and Palladium Cooperative Dual-Catalytic Cross-Coupling Systems

Double-label crossover, modified substrate, and catalyst comparison experiments in the gold and palladium dual-catalytic rearrangement/cross-coupling of allenoates were performed in order to probe the mechanism of this reaction. The results are consistent with a cooperative catalysis mechanism whereby (1) gold activates the substrate prior to oxidative addition by palladium, (2) gold acts as a carbophilic rather than oxophilic Lewis acid, (3) competing olefin isomerization is avoided, (4) gold participates beyond the first turnover and therefore does not serve simply to generate the active palladium catalyst, and (5) single-electron transfer is not involved. These experiments further demonstrate that the cooperativity of both gold and palladium in the reaction is essential because significantly lower to zero conversion is achieved with either metal alone in comparison studies that examined multiple potential gold, palladium, and silver catalysts and precatalysts. Notably, employment of the optimized cocatalysts, PPh3AuOTf and Pd(2)dba(3), separately (i.e., only Au or only Pd) results in zero conversion to product at all monitored time points compared to quantitative conversion to product when both are present in cocatalytic reactions.