A chemoenzymatic synthesis of 2-bromo-6-hydroxy-3-methoxy-2-cyclohexen-1-one starting from cyclohexane-1,3-dione is reported. Manganese (III) acetate-mediated acetoxylation followed by the enzyme-mediated hydrolysis of alpha'-acetoxy enone affords hydroxy-enone 5 and enone 4 with high enantiomeric excesses in good yields.