Stereoselective Synthesis of <i>cis</i>- and <i>trans</i>-3,4-Dihydro-3,4,8-trihydroxynaphthalen-1(2<i>H</i>)-one

A short and efficient protocol for the stereoselective synthesis of racemic <i>trans</i>- and <i>cis</i>-3,4-dihydro-3,4,8-trihydroxynaphthalen-1(2<i>H</i>)-one (<b>1</b> and <b>2</b>, resp.), is described, comprising nine and eight steps starting from commercial juglone (=5-hydroxynaphthalene-1,4-dione; <b>12</b>) (<i>Scheme 4</i>). Furthermore, an attempt to obtain <b>1</b> and <b>2</b> via phthalide annulation as the key step (<i>Schemes 2</i> and <i>3</i>) and a regioselective oxidation of the intermediate 1,2,3,4-tetrahydronaphthalene-1,2,4,5-tetrols <b>27</b> and <b>28</b> with activated MnO₂ were carried out (<i>Scheme 4</i>).