[Cr(CO)3(naphthoquinone)](1), prepared in a three-step sequence starting from 1,4-dihydroxynaphthalene, was reduced to the corresponding meso-dihydronaphthalene syn-diol complex and the latter was desymmetrized to give the mono-acyl complex with 99% ee via asymmetric acylation catalyzed by the two new and easily accessed chiral diamines 7 and 8.