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 Pd is key for the efficient transformation.
Bibliographical noteKAUST Repository Item: Exported on 2020-10-01
Acknowledgements: P.E.K. thanks the Deutsche Bundesstiftung Umwelt for a doctoral stipend. The research leading to these results has received funding from the European Research Council under the European Union's Seventh Framework Programme (FP/2007–2013)/ ERC Grant Agreement no. 617044 (SunCatChem). B.M., C.Z. and L.C. acknowledge King Abdullah University of Science and Technology (KAUST) for computational resources of the supercomputer Shaheen II.