| This dissertation describes my research under the guidance of Professor James L. Leighton which has resulted in development of tandem carbonylation-allylation methods to synthesize polyketide triols. The rhodium-catalyzed silylformylation of homoallylic alcohol-derived diallylsilanes generates a β-silyl aldehyde which undergoes a spontaneous uncatalyzed intramolecular allylsilylation. Tamao oxidation of the tandem silylformylation-allylsilylation product affords 1,3,5-syn,syn-triols.; Incorporation of geometrically defined crotyl groups on silicon and the corresponding tandem silylformylation-crotylsilylation reaction affords 1,3,5- syn,syn-triols with the stereospecific incorporation of an allylic methyl group. As part of these studies, a new method for the selective monoalcoholysis of dihydrosilanes has been developed. Iterative application of this reaction sequence rapidly generates complex polyketide structures.; The polyketide structures resulting from these reactions have been utilized as scaffolds for the target- and diversity-oriented synthesis of polyketide macrolides. The strategies developed expand the utility of these reactions and their products beyond the iterative application. A review of the major strategic approaches to the synthesis of polyketides to date is also presented. |
