Regiodivergent Carbonylation of Alkenes: Selective Palladium-Catalyzed Synthesis of Linear and Branched Selenoesters

An unprecedented regiodivergent palladium-catalyzed carbonylation of aromatic alkenes has been developed. Utilizing commercially available Pd(CH3CN)2Cl2 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. The first regioselective selenocarbonylation of alkenes is reported. This general protocol provides a variety of branched and linear selenoesters with wide functional group compatibility and tunable regioselectivity.+image