Developing Electroreductive Methodologies via a Radical-Polar Crossover Pathway

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Abstract
Electroorganic synthesis is an enabling technology for modern organic chemistry owing to its sustainability, versatility, and unique selectivity. Since its initial invention in the nineteenth century, synthetic electroorganic chemistry has been considerably shaped by the advances in electroanalytical techniques, reactor design and theoretical developments. To date, electrochemistry represents one of the most intimate and powerful means to generate reactive intermediates and has been applied in a variety of transformations from inert bond activation to complex molecular synthesis to polymer growth. Electrochemistry is also used to probe the mechanism of organic transformations through electroanalytical measurements and can be merged with other novel strategies to realize orthogonal reactivity.In this dissertation, we begin with an overview of the historical development of electroorganic synthesis. We then showcase the unique features of electrochemistry with state-of-the-art examples. Specifically, we are interested in developing electroreductive reactions that are previously prone to inherent limitations. In the first example, we demonstrated the electroreductive activation of Si-Cl bond to generate reactive silyl radicals at deeply reducing potentials. Thorough mechanistic studies revealed a radical-polar crossover mechanism, which guided the development of silacycle synthesis, hydrosilylation and allylic silylation. Subsequently, this mechanistic design was employed in the dialkylation reaction, where we utilized electrochemistry’s ability to distinguish minute differences of the reduction potentials of alkyl halides to achieve their selective addition to alkenes. In a similar fashion, we successfully demonstrated the cross-electrophile coupling of two alkyl halides aided by cyclic voltammetry and computational studies. Drawing inspiration from Mg batteries, we used dimethoxyethane to solubilize the Mg salt passivation layer in the alkyl halides involved reactions and achieved excellent scalability. Finally, an electrooxidative alkene chlorophosphinoylation was performed guided by the principle of anodically couple electrolysis. This modular strategy shows the precise control of electrocatalysts over the selective formation and downstream reactivity of reactive intermediates.
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442 pages
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2022-08
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Alkene Difunctionalization; Electrochemistry; Electroorganic Synthesis; Organic Chemistry; Radical-Polar Crossover; Reduction
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Lin, Song
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Abruna, Hector D.
Collum, Dave
Degree Discipline
Chemistry and Chemical Biology
Degree Name
Ph. D., Chemistry and Chemical Biology
Degree Level
Doctor of Philosophy
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dissertation or thesis
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