Total syntheses in the pederin family: Total synthesis of pederin, pederone and mycalamide B; progress toward the synthesis of onnamide F and psymberin

The pederin family of natural products has been the subject of numerous synthetic efforts because of a combination of intricate, complex structures, and high levels of biological activity. The first chapter of this dissertation reviews previous syntheses in the family. The following chapters discuss our own work toward 5 different members. The routes are highlighted by a diastereoselective formal hetero-Diels-Alder reaction, diastereoselective Mukaiyama-Michael reaction, and novel coupling strategies that allow for concise diastereoselective syntheses with no degradation of stereogenic information. These expedient routes, starting from commercially available chiral epoxides, have resulted in the asymmetric total syntheses of pederin (12 step longest linear sequence), pederone (11 step longest linear sequence), and mycalamide B (14 step longest linear sequence). Additionally several routes to potential coupling partners for onnamide F are discussed. Finally, preliminary studies toward the synthesis of psymberin are reported.