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 enone with high enantiomeric excesses and in good yields. The reduction of the acetoxy enones furnished both enantiomers of 4-acetoxy-2-hydroxymethyl-cyclohex-2-en-1-one in high enantiomeric excess.