Abstract: The total syntheses of the perylenequinone natural products phleichrome and calphostin A are detailed. The syntheses were based on (1) the de novo construction of regiospecifically oxygenated and selectively protected naphthalene subunits,(2) the enantiospecific introduction of the stereogenic side chains using a chiral (a-alkoxyalky1)- lithium reagent, and (3) a highly atropdiastereoselective Cu (1)-promoted biaryl synthesis ...