Doctor of Philosophy
Dr. Michael A. Kerr
The first chapter of this thesis focuses on the synthesis and reactivity of cyclopropane hemimalonates. The cyclopropane hemimalonates can easily be synthesized from 1,1-cyclopropanediesters. The reactivity of cyclopropane hemimalonates with indole under ultra-high pressure conditions leads to ring opened adducts that are complementary to previous research in the Kerr group. The tandem ring opening decarboxylation reaction of cyclopropane hemimalonates led to the synthesis of γ-aminobutyric acid analogues. When an external nucleophile was not present, the cyclopropane hemimalonates could rearrange to form butyrolactones in good to excellent yields. The stereochemical integrity of the cyclopropane hemimalonate is retained through this process, which is not usually seen in cyclopropane reactivity.
The second chapter describes the progress towards the synthesis of Kainic acid. While the progress towards this natural product appeared to be going well, after closer analysis of the products, a new reactivity of diazo species and cyclopentadiene was realized.
In the third chapter, the progress towards the synthesis of Actinophyllic acid is provided. Synthesis of advanced intermediates was completed, however the key formation of a 1,4-dicarbonyl species of the pyrrolidine ring eluded this study.
Emmett, Michael R., "The Synthesis and Reactivity of Novel Donor-Acceptor Cyclopropanes and Progress Towards Pyrrolidine Alkaloids" (2014). Electronic Thesis and Dissertation Repository. 2267.