Asymmetric Total Synthesis of Brasiliquinones B and C via Oxidative Cyclization of a Hydroquinone-Silyl Enol Ether Hybrid

The asymmetric total synthesis of angucycline antibiotics (S)-brasiliquinones B and C was accomplished. The benz[a]anthraquinone core was constructed via oxidative cyclization of a hydroquinone-silyl enol ether hybrid. The resultant pentacyclic acetal was converted to the silyl enol ether, which was treated with Pd(II)/O-2 to afford brasiliquinone C, after multistep conversion including dehydrogenation, desilylation and deacetalization, and hydroquinone oxidation. The (S)-configuration of natural brasiliquinones was confirmed based on the stereochemical correlation with the synthetic products.

Automated summary

The asymmetric total synthesis of angucycline antibiotics (S)-brasiliquinones B and C was achieved by constructing the benz[a]anthraquinone core through oxidative cyclization. The synthetic products confirmed the (S)-configuration of natural brasiliquinones.