An　unprecedented　base-metal-catalyzed　oxidative　cross-coupling　between　2-naphthols　and　phenols　or　arylamines　has　been　described　in　this　report.　Acetic　acid　and　2,2,6,6-tetramethylpiperidine-1-oxyl　(TEMPO)　are　the　crucial　oxidative　system　that　promotes　the　transformation　under　aerobic　conditions　with　the　assistance　of　base-metal　salts.　While　ferrous　sulfate　was　the　optimal　catalyst　in　the　oxidative　coupling　of　2-naphthols　and　phenols　to　produce　4-aryloxynaphthalene-1,2-diones,　cuprous　iodide　catalyst　is　utilized　to　synthesize　(arylimino)naphthalen-1(4H)-ones　from　2-naphthols　and　arylamines.　Employing　this　protocol,　molecule　skeletons　similar　to　tanshinones,　2-(2-carboxyvinyl)benzoic　acid　and　neo-tanshinlactone　can　be　accessed　thus　highlighting　its　potential　use　in　organic　synthesis　and　drug　discovery.　©　2025　Wiley-VCH　GmbH.