Enantioselective Synthesis of Azamerone

A concise
and selective synthesis of the dichlorinated meroterpenoid
azamerone is described. The paucity of tactics for the synthesis of
natural-product-relevant chiral organochlorides motivated the development
of unique strategies for accessing these motifs in enantioenriched
forms. The route features a novel enantioselective chloroetherification
reaction, a Pd-catalyzed cross-coupling between a quinone diazide
and a boronic hemiester, and a late-stage tetrazine [4+2]-cycloaddition/oxidation
cascade.