Prebiotic inspiration to functional application: Synthetic and mechanistic investigations of glyoxylate and its formal dimer dihydroxyfumaric acid
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Ward, George William
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Abstract
The origins of life on earth has been a topic of study in the scientific community for many years. In recent decades, as an understanding of biochemistry developed, how the biomacromolecules that make up life were formed became a prominent question. Exhibiting plausible routes to generate these compounds from simple building blocks and under conditions that could reasonably have existed on the early earth is the focus of prebiotic chemists. Among the small building blocks of interest, glyoxylate along with its dimer dihydroxyfumaric acid (DHF), have been of particular interest. In this thesis, both glyoxylate and DHF are studied with the goal of both showing the possibility of prebiotic functions as well as taking novel chemistries discovered toward origins of life work and expanding them into functionally applicable methodologies for synthetic chemists. The physical organic properties of DHF are analyzed both experimentally and computationally followed by expansion of DHF nucleophilic chemodivergent reactivity to (hetero)aryl aldehydes is shown based on choice of base and solvent. Novel decarboxylation reactivity is used to synthesize the natural product C-veratroylglycol in a single step and is being used toward the synthesis of related lignan and neo-lignan natural products. Glyoxylate is investigated for its possibility to serve a prebiotic precursor to the phosphodiester linker in nucleic acid polymers. Results from these studies lead to a pivot of using glyoxylate derived mixed acetals as a novel alcohol protecting group. This work exhibits how prebiotic chemistry can be applicable to more than just origins of life chemistry and can be used to inspire new synthetic methodologies and syntheses.
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2018-11-09
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Dissertation