Date of Award

2018

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

First Advisor

Matthias Brewer

Second Advisor

Adam Whalley

Abstract

Aldol cyclotrimerizations have been used to achieve the rational chemical synthesis of both fullerenes and fullerene fragments in the past. Under certain conditions this reaction produces the corresponding cyclotetramer which has sometimes been regarded as an undesired byproduct. This work details efforts to synthesize and use these cyclotetramers toward a synthesis of a C240 fullerene fragment. One principal focus in this work is tridecacyclene, a cyclic tetramer of acenaphthylene given its name by our group for its thirteen rings. Relatively low yields for the synthesis of tridecacyclene and its derivatives drove us to investigate the mechanism of its formation and attempt to optimize its production. During this process, novel dione products were isolated from the attempted cyclotetramerization of two dimeric species. Characterization of these products by X-ray crystallography gave valuable insight into the reaction pathway, leading us to a new proposed mechanism of formation for the cyclotetramerization products observed in these aldol reactions.

β-hydroxy-α-diazoketones are suitable progenitors to vinyl cation intermediates whose use in chemical synthesis is relatively unexplored. As part of an extensive project to develop the chemistry of vinyl cations for use in carbon-carbon bond forming reactions to build important molecular scaffolds, a range of β-hydroxy-α-diazoketones containing a pendent nucleophilic alkene were synthesized. Treatment of these compounds with Lewis acids gave either lactone or cyclopentenone products depending on the substrate used. Proposed herein is a mechanism involving a key acylium intermediate which, depending on the position of the pendent alkene, results in different product outcomes.

In a collaborative effort to further investigate the known anti-cancer properties of fusarochromanone, a fungal metabolite that is isolated from Fusarium-infected feed from cold climates, a large-scale synthesis of this natural product was explored. An efficient, scalable synthesis of the previously prohibitively expensive amidochromanone starting material has been achieved and its elaboration to fusarochromanone has been demonstrated.

Language

en

Number of Pages

235 p.

Available for download on Thursday, July 30, 2020

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