Discovery and Synthesis of Boletopsins 13 and 14, Brominated Fungal Metabolites of Terrestrial Origin.

Here we report the discovery and synthesis of complex polybrominated p-terphenyl ethers isolated from a mushroom (Boletopsis sp.) used as a traditional medicine by the Kiovi people in the highlands of Papua New Guinea. Boletopsins 13 and 14 represent the first report of polybrominated fungal metabolites to be produced by a terrestrial fungus. The synthetic method employs 2,4,4,6-tetrabromo-2,5-cyclohexadienone to achieve selective polybromination of the extended aromatic system in a selective and sequential manner.