A chemoenzymatic synthesis of both enantiomers of the pharmacologically interesting 4- acetoxy-2-hydroxymethyl-cyclohex-2-en-1-one starting from cyclohexane-1, 3-dione is described. Cyclohexane-1, 3-dione was converted into 4, 6, 7, 8-tetrahydro-benzo [1, 3] dioxin-5-one and then manganese (III) acetate-mediated acetoxylation followed by the enzyme-mediated hydrolysis of α-acetoxy enone afforded the acetoxy enone and hydroxy ...