The reaction of BunLi with either syn- or anti-n6-(1-acetoxycyclobutabenzene)Cr(CO)3 generates under mild conditions the planar chiral ortho-quinodimethane complex intermediate 4 which reacts with dienophiles (methyl acrylate, acrylonitrile, dimethyl fumarate) highly stereoselectively from the face opposite the metal to give the anti-1-hydroxytetrahydronaphthalene–Cr(CO)3 complexes (X-ray structures of 5 and 6) and, after decomplexation, the 1-hydroxytetrahydronaphthalenes 7–14(asymmetric synthesis of 7 and 8).