Oxidative Dearomatization / Diels-Alder Approaches to Maoecrystal V and the Gibberellin Family of Natural Products

Abstract

Synthetic approaches to the complex natural product maoecrystal V and the gibberellin family of natural products are presented. The two approaches are united by an oxidative dearomatization / intramolecular Diels Alder strategy for the construction of [2.2.2]- bicyclooctenes. Chapter 1 highlights previous synthetic approaches for the synthesis of maoecrystal V and Chapter 2 chronicles my efforts toward a double-Diels-Alder approach toward maoecrystal V. In the course of investigating a hetero-Diels-Alder strategy for construction of maoecrystal V’s tetrahydrofuran ring several fragmentation and rearrangements of the [2.2.2]-bicyclooctene core were encountered. One of these, a novel skeletal rearrangement from [2.2.2] to [3.2.1]-bicyclooctene, was then utilized for entry into the gibberellin family of natural products. Chapter 3 discusses previous syntheses of gibberellins while Chapter 4 details my entry into this family of natural products and further exploration of the novel skeletal rearrangement. Chapter 5 discusses my contributions to the field of bicyclic and tricyclic guanidine synthesis. Finally, Chapter 6 highlights my work related to pharmaceutical drug analysis, focusing on less commonly utilized elemental substitutions.