Organic Chemistry

Total Synthesis of Peshawaraquinone



A concise synthesis of a stereochemically complex meroterpenoid, peshawaraquinone, via the unsymmetrical dimerization of its achiral precursor, dehydro-alpha-lapachone, is reported. Enabled by reversible oxa-6pi-electrocyclizations of (2H)-pyran intermediates, the base-catalyzed dimerization sets up an intramolecular (3+2) cycloaddition, with the formation of six stereocenters during the cascade. Combining the synthesis and in situ dimerization of dehydro-alpha-lapachone allows a one-step total synthesis of peshawaraquinone from lawsone and prenal.


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Supplementary material

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Supporting Information
Experimental procedures and characterization data for all compounds, and coordination geometries for DFT optimized intermediates.