Abstract We report the metal-catalyzed α-hydroxylation of a variety of cyclic and acyclic β- dicarbonyl compounds by molecular oxygen. The decisive advantage of this new method is the use of catalytic amounts of the nontoxic cerium salt CeCl 3· 7H 2 O in 2-propanol at ambient temperature. Most of the cyclic substrates 4a− 4i give high yields of analytically pure products 5a− 5i, and the workup procedure is simple filtration through silica gel. The ...