A Proposal for the Mechanism-of-Action of Diazoparaquinone Natural Products

Abstract

Treatment of the representative diazoparaquinone prekinamycin dimethyl ether with Bu3SnH/AIBN in aromatic solvents furnishes moderate-to-good yields of formal aryl adducts wherein a molecule of solvent is attached to the carbon (C(11)) previously bearing the diazo function. Substituent studies provide evidence in support of a radical aromatic substitution mechanism, in which radical addition to the diazoparaquinone function generates an intermediate C(11) vinylic radical.