In this protocol we described an environmentally friendly synthesis of α-arylated cyclic β-dicarbonyl compounds employing various catechols as precursors through an oxidation/Michael addition sequence. The process proceeded under the catalysis of a commercially available laccase at room temperature with the use of aerial oxygen as the oxidant affording the products in moderate to excellent yields (36–96%). Furthermore, a highly functionalized cyclopentane bearing an all-carbon quaternary stereogenic centre was synthesized through the arylation in excellent diastereoselectivity (dr > 99 : 1, 95% ee).