Graduate Thesis Or Dissertation
 

Part I: Synthetic Studies Towards Viridin, Halenaquinone, and Obtusanal. Part II: Analysis, Synthesis, and Characterization of Coronene Derivatives.

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  • This thesis is separated into three distinct projects. First, synthetic studies towards the furanosteroid viridin shown in part I. Second, synthetic studies towards the diperene obtusanal shown in part II. Third, the analysis, characterization, and synthesis of coronene derivatives towards their application in organic batteries shown in part III. Significant synthetic progress towards viridin has been made in our laboratory. We showcased the first total synthesis directed application of a proline sulfonamide-catalyzed, asymmetric Yamada-Otani cyclization as a key step to enantioselectively form the A ring of viridin from acyclic achiral aldehyde and enone precursors. In addition, we demonstrate an unprecendented, palladium-mediated oxidative furan formation to install the hallmark furan moiety from a diol and alkene functional groups. Significant progress towards obtusanal has been made in our laboratory culminating in the synthesis of the complete carbon bicyclic scaffold of obtusanal. In addition to using a common synthetic intermediate from the viridin project, we established several key transformations. First, a sequential two-step palladium-catalyzed functionalization of the bromo,chloro aromatic moiety. We successfully functionalized the aromatic moiety in high yield across multiple substrates through a Negishi cross-coupling selectively for the aryl bromide with minimal β-hydride elimination, followed by a palladium-catalyzed oxygenation of the aryl chloride. Second, we show a biomimmetically-inspired intramolecular aldol cyclization to set the complete scaffold of obtusanal as a single diasteromer. The intramolecular aldol reaction appears to be mediated by silica gel on an intermediate bearing a silyl enol ether and aldehyde functionality. The dense and functionally diverse structure of the intermediates leading to obtusanal necessitated careful reagent selection and intermediate functional group selection. All told, we examined five separate approaches towards obtusanal, and synthetized an advanced intermediatebranched from the second generation “OMe series” sequence, differing from obtusanal only by differing a C6 alkene versus aldehyde, and C12-OMe verses OAc. We report the synthesis of a new carbonylated PAH coronenehexaanhydride to be used as a cathode material in batteries and conducted NMR analysis of the coronene-based materials within organic batteries. We were able to produce coronenehexaanhydride over two steps from coronene; however, application of the material by the Ji laboratory reported low voltage potential for the material. Despite this setback, coronene was identified as a superior cathode material by the Ji laboratory, and NMR analysis prior and post discharge was conducted by our laboratory, which indicated no covalent changes to coronene.
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