Enantioselective Total Synthesis of (−)-Diversonol

For the synthesis of (−)‐diversonol (ent‐1), an enantioselective domino‐Wacker/carbonylation/methoxylation reaction and an enantioselective Wacker oxidation were used to give the chroman in high yield and 96 % and 93 % ee, respectively. Dihydroxylation at the vinyl moiety using the Sharpless procedure and a Wittig–Horner reaction followed by hydrogenation, benzylic oxidation, and an intramolecular acylation provided the tetrahydroxanthenone, from which ent‐1 is accessible in a few steps. Furthermore, the synthesis of the diastereomeric diversonol rac‐1,9 a‐epi‐diversonol (rac‐41) is also described. Domino at its best: An enantioselective domino‐Wacker/carbonylation/methoxylation reaction was performed in the total synthesis of the fungal metabolite diversonol (see scheme). Furthermore, synthesis of diastereomeric rac‐1,9a‐epi‐diversonol is also described.