Total Synthesis of (-)-Preussochromone A.

An enantioselective total synthesis of the natural product (-)-preussochromone A is reported. The tricyclic thiopyrane skeleton could be assembled via Lewis acid-mediated cycloisomerization of a precursor with a 2-thiochromenone substructure and an α-ketoester moiety. The chromenone core was synthesized by cyclization of a dithioketene acetal and oxidation to a 2-sulfonylchromenone to set up the subsequent thia-Michael--Michael addition of an aliphatic thiol producing the highly oxidized side chain.