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4-Hydroxycoumarin (1) is a useful synthon in synthetic organic chemistry and a basic skeleton of several bioactive compounds. The direct functionalization of 1 with novel catalytic system would provide an efficient meaning for construction of a chemical library. Here, we developed a new catalytic system using palladium(II) acetate for the C3 regioselective mono-arylation of 1. The 3-mono-arylated...