Electronic Thesis and Dissertation Repository

Degree

Doctor of Philosophy

Program

Chemistry

Supervisor

Michael A. Kerr

Abstract

The first chapter of this thesis consists of two related projects that explore novel reactivity of donor-acceptor cyclopropanes, specifically 2-substituted cyclopropane 1,1-diesters. The first project involves the nucleophilic ring opening of donor-acceptor cyclopropanes with potassium organotrifluoroborates. It was found that during the ring opening of the cyclopropane, the diesters of the cyclopropane formed a malonyl-BF2 complex. The complex could then be hydrolyzed to afford substituted malonates. The reaction was limited to aryl cyclopropanes and potassium alkynyltrifluoroborates. The second project in this chapter explores modifying the Kerr group’s previous synthesis of tetrahydro-1,2-oxazines, such that geminal allyl, methyl esters are now on the tetrahydro-1,2-oxazine. This allows for a one-pot dehydrocarbonylation/dehydration procedure to access pyrroles.

The second chapter of this thesis describes efforts towards the total synthesis of two natural products via Diels-Alder of quinoid species. The first project describes the formal synthesis of indole containing fargesine utilizing the Kerr group’s Diels-Alder/Plieninger indolization sequence. A Pinnick oxidation, followed by a Curtius rearrangement was required to complete the formal synthesis. The second project describes efforts towards benzofuranone containing fumimycin. The benzofuranone would be accessed by the Diels-Alder of requisite benzoquinone ketal and diene. Following a similar protocol to the Kerr group’s modified Plieninger indolization sequence could allow access to the core of fumimycin. Despite many alternate routes, formation of the benzofuranone core eluded this study

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