STUDIES IN TOTAL SYNTHESIS OF GELSEMIUM ALKALOIDS AND SYNTHESIS OF KETOHYDROPEROXIDES

Gelsemium plants have been used as traditional Chinese medicines since the 16th century documented with their potent biological activities. The remarkable medicinal potential of these plants is largely attributed to their abundant alkaloids. Because of their complex architecture, potent biological activities, and limited accessibility, these alkaloids have attracted significant synthetic attention. The synthetic approach toward gelsefuranidine was explored, laying a solid foundation for the our later synthesis of gelsevirine and gelsemine. Through the careful design of model experiments and DFT calculations to examine the feasibility of a novel photo-induced thiyl-radical catalyzed (3+2) cycloaddition, we completed the first total synthesis of gelsevirine and the synthesis of gelsemine.We have also explored the synthesis of combustion-relevant ketohydroperoxide species. Using an improved Caglioti hydroperoxidation protocol, we successfully synthesized a ketohydroperoxide species on a multigram scale. Several synthetic approaches toward ketohydroperoxide species were explored. We also examined the preliminary compatibility of a 1,1-bisperoxyacetal platform to generally access smaller ketohydroperoxide species. We believe this engineered platform could greatly streamline the combustion studies of these metastable compounds.