Direct Displacement of Alkoxy Groups of Vinylogous Esters by Grignard Reagents and Studies Toward the Total Syntheses of Natural Products

The development of novel synthetic methodology and the total synthesis of natural products are essential mainstays of organic chemistry. The development of novel synthetic methodology to accomplish new molecular transformations is of great importance to organic chemistry. As well, total synthesis of natural products commands significant interest because of the vast potential many natural products possess for beneficial medicinal application. In the exploration of natural products, total synthesis substantially empowers the researcher who seeks to reassign natural product structures that have been misassigned. This dissertation incorporates both novel synthetic methodology and total synthesis through the trajectory of three distinct projects. Chapter one describes the significant advances made in the carbon-carbon bond forming reaction produced by the direct displacement of alkoxy groups of vinylogous esters by Grignard reagents. Applications of this reaction have shed light on interesting carbonyl reactivity. Increased mechanistic understanding of this displacement reaction has been achieved through a meld of theoretical computation and physical experimentation. Chapter two addresses the significant progress made toward the total synthesis of the complex natural products chrysophaentins A and E. These molecules are compelling targets for investigation not only because of the novel antibiotic potential that chrysophaentin A features but also because of the natural products' structural uniqueness. Chapter three expounds on the progress made toward the total synthesis of erythroculine N-oxide with the goal of revising the likely misassigned reported structure of the natural product jamtine N-oxide.