The direct arylation of 1,3‐benzodioxole and 2,2‐difluorobenzo[1,3]dioxole with 26 different aryl bromides yields the respective 4‐substitued products in yields of >80% requiring between 0.05–1 mol % Na₂PdCl₄, 30 mol % pivalic acid, 1.3 equivs. K₂CO₃ and ca. 250 equivs. of diethylacetamide per Pd at T =120 °C. The nature of the amide and the concentration of the reactants are crucial for the optimization of the reaction conditions. The primary role of the acetamide is that of a ligand to Pd, it is not needed as a solvent.
