Facile synthesis of naphthoquinone spiroketals by diastereoselective oxidative [3+2] cycloaddition

A highly selective oxidative [3 + 2] cycloaddition of chiral enol ethers and hydroxynaphthoquinone is described. This convergent strategy is amenable to an enantioselective synthesis of beta-rubromycin and related naphthoquinone spiroketals. Several compounds were found to inhibit DNA-polymerase and telomerase in a manner resembling a-rubromycin and beta-rubromycin.