Remote Regiocontrol by a Thioether Group in Diels−Alder Reactions of Naphthazarin: Regioselective Access to Tetracyclic Polyhydroxyquinones

Abstract
The synthesis of tetracyclic polyhydroxyquinones 5a and 5b was achieved through a sequence involving two Diels−Alder reactions with 1-methoxy-1,3-cyclohexadiene: the first with 2-(p-tolylthio)naphthazarin and the second on the resulting tricyclic derivative previously transformed into a (p-tolylsulfinyl)naphthazarin. The success of this strategy stemmed from the efficient remote regiocontrol exerted by the thioether substituent in the first step.