Synthesis of Organic Building Blocks and Synthetic Strategies Toward Aleutianamine

Author: Sercel, Zachary Patrick

Year: 2023

Degree: Dissertation (Ph.D.)

Advisor: Stoltz, Brian M.

Committee Members: Robb, Maxwell J.; Gray, Harry B.; Reisman, Sarah E.; Stoltz, Brian M.

Option: Chemistry

DOI: 10.7907/3ezw-2h57

Abstract

Described herein are the development of the palladium-catalyzed decarboxylative asymmetric allylic alkylation of medicinally relevant 5- and 7-membered diazaheterocycles and efforts toward the total synthesis of the cytotoxic pyrroloiminoquinone marine alkaloid aleutianamine. The former methodology provides a new tactic to incorporate Csp3 structural complexity into future lead compounds containing diazepane and imidazolidine moieties. The latter project is ongoing.

Additionally, Chapter 3 discusses preliminary attempts to improve the synthetic accessibility of minimally substituted corroles, which were conducted during a research internship in the laboratory of Prof. Zeev Gross at the Technion. During the course of this research, the first example of a β-unsubstituted free base monoazaporphyrin was isolated, and its cobalt complex was characterized by x-ray crystallography.

Finally, Appendix 8 presents a series of cationic and radical-mediated fragmentations of a derivative of (+)-3-Carene, a chiral pool material. These experiments led to the observation and mechanistic study of an unexpected rearrangement.

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