Oxidative Addition to Palladium(0) Made Easy through Photoexcited‐State Metal Catalysis: Experiment and Computation

Visible‐light induced, palladium catalyzed alkylations of α,β‐unsaturated acids with unactivated alkyl bromides are described. A variety of primary, secondary, and tertiary alkyl bromides are activated by the photoexcited palladium metal catalyst to provide a series of olefins at room temperature under mild reaction conditions. Mechanistic investigations and density functional theory (DFT) studies suggest that a photoinduced inner‐sphere mechanism is operative in which a barrierless, single‐electron transfer oxidative addition of the alkyl halide to Pd0 is key for the efficient transformation.