Electrophilic aromatic prenylation via cascade cyclization

To gain access to prenylated hexahydroxanthenes, tandem cascade cyclization–electrophilic aromatic substitution reactions have been studied on substrates bearing allylic and propargylic substituents. Both BF 3 ·OEt 2 and TMSOTf can be used to initiate this reaction sequence, resulting in different ratios of the C-2 and C-6 substitution products. Even though allylic transposition is observed in some cases, the results of a crossover experiment are consistent with an intramolecular reaction sequence. Taken together, these studies now allow preparation of either the C-2 or C-6 prenylated hexahydroxanthene products.