The article gives a brief outline of the rediscovery of tetrahydronaphthalene-1,4-dione, a stable tautomer which has been known for over half a century but has not been applied in synthesis. Desymmetrization is readily achieved via enantioselective reduction. Synthetic potential apart, the dione and its chromiumtricarbonyl complex are of theoretical interest. Thus, whereas dihydroxynaphthalene requires quite harsh conditions and leads to a 1:1 mixture of the two tautomers, the chromiumtricarbonyl complex of dihydroxynaphthalene tautomerizes under very mild conditions to the tetrahydronaphthalene-1,4-dione complex. An earlier literature report showed that in trifluoroacetic acid, the dione tautomer is present exclusively. This has now been used to isolate multigram quantities of the compound.