The Development of Ni-Catalyzed Methods for Application in Total Synthesis

Citation

Shimozono, Alexander Mitsuo (2023) The Development of Ni-Catalyzed Methods for Application in Total Synthesis. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/h0w0-1d25. https://resolver.caltech.edu/CaltechTHESIS:11032022-004822338

Abstract

The total synthesis of complex natural products often requires the development of mild, selective transformations. Once developed, these methods can serve as starting points for related methodologies, fundamental mechanistic studies, or applied in other total syntheses. Herein, a series of projects that embody this relationship are described. Inspired by unexpected challenges in the synthesis of complex diterpenoid alkaloid talatisamine, a Ni-catalyzed enol-triflate-halogen exchange reaction was developed. In addition to finding application toward the synthesis of talatisamine, this reaction found further use in an attempted route toward enmein-type ent-kauranoid natural products. En route to the synthesis of these natural products, a need for meso-anhydride functionalization was identified which inspired a research program dedicated to Ni-catalyzed reductive functionalization of anhydrides.

Thesis Files