| The total synthesis of several dimeric naphthoquinone natural products is described. The efforts of this work culminated in the completed total synthesis of rubionoclin B, rubicordifolin, microphyllaquinone, mollugin, and rubifolin. These syntheses feature new modes of reactivity based on a facile tautomerization of alkyl substituted quinones. These include a tautomerization/electrocyclization strategy that was developed for the synthesis of chromene natural products and a tautomerization/Diels-Alder cascade that was developed for the synthesis of chroman natural products.;In addition to these completed syntheses, significant progress has been made in the total synthesis of rubioncolin A. Evaluation of two alternative approaches to the natural product provided insight that will guide further strategies. These efforts included an intermolecular Diels/Alder cycloaddition and an electrocyclization reaction.;In addition to this experimental work, computational methods were developed for the evaluation of a synthesis of exiguamines A and B. This work culminated in a rapid, potentially biomimetic total synthesis of these two natural products. |
