A Bio-Inspired Synthesis of Peshawaraquinone

A ten-step bio-inspired enantioselective synthesis of peshawaraquinone, an uncommon and complex naphthoquinone mero-terpenoid is described. Key to the success of this synthetic pathway is a well-tuned HFIP-promoted metal-free allylation was developed to coupling lawsone with allylic alcohols, together with an usual organo-catalyzed [3+2] cycloaddition for con-structing the bicyclo[3.2.1]octane core structure. Further investigation disclosed peshawaraquione is a racemic mixture.