Matthias Beller

An unprecedented regiodivergent palladium‐catalyzed carbonylation of aromatic alkenes has been developed. Utilizing commercially available Pd(CH 3 CN) 2 Cl 2 in the presence of 1,1′‐ferrocenediyl‐bis( tert ‐butyl(pyridin‐2‐yl)phosphine) ligand L8 diverse selenoesters are obtained in a straightforward manner. Key to success for the control of the regioselectivity of the carbonylation step is the concentration of the acidic co‐catalyst. This general protocol features wide functional group compatibility and good regioselectivity. Mechanistic studies suggest that the presence of stoichiometric amounts of acid changes the properties and coordination mode of the ligand leading to reversed regioselectivity.