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Please use this identifier to cite or link to this item: http://arks.princeton.edu/ark:/88435/dsp014j03d286d
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dc.contributor.advisorKnowles, Robert R
dc.contributor.authorShin, Nick Youngmu
dc.contributor.otherChemistry Department
dc.date.accessioned2022-10-10T19:52:35Z-
dc.date.available2023-10-02T12:00:06Z-
dc.date.created2022-01-01
dc.date.issued2022
dc.identifier.urihttp://arks.princeton.edu/ark:/88435/dsp014j03d286d-
dc.description.abstractFree radicals are often considered high-energy and fleeting intermediates. Controlling their reactivity remains a great challenge in organic synthesis. My graduate work centers on using proton-coupled electron transfer (PCET) as a general strategy for developing radical transformations with high selectivities and unprecedented reactivities. In these reactions, stepwise or concerted transfer of electron and proton serves as a key process to activate organic molecules and achieve selective catalysis.In Chapter 1, I describe developing a catalytic strategy for the light-driven deracemization of cyclic urea. Deracemization is a process where a racemic mixture is converted into a single enantiomer of the same molecule. Despite its synthetic benefits for late-stage stereo-correction, catalytic protocols for deracemization remain extremely rare. To this end, we developed a ternary catalyst system that enables photocatalytic deracemization. Excellent enantioselectivity is achieved for the homolysis and reformation of a stereogenic C–H bond through orchestrated movements of an excited-state electron, proton, and hydrogen atom. In Chapter 2, I report a novel strategy for the homolysis-enabled electronic activation of aryl electrophiles. While heteroatom-centered radicals are known to be highly electrophilic, their ability to serve as transient electron-withdrawing groups and facilitate polar reactions at distal sites has not been extensively studied. In this work, we describe a strategy for the electronic activation of halophenols, wherein homolysis of the aryl O–H bond enables direct nucleophilic aromatic substitution of otherwise inert aryl halides with carboxylate nucleophiles under mild conditions.
dc.format.mimetypeapplication/pdf
dc.language.isoen
dc.publisherPrinceton, NJ : Princeton University
dc.relation.isformatofThe Mudd Manuscript Library retains one bound copy of each dissertation. Search for these copies in the library's main catalog: <a href=http://catalog.princeton.edu>catalog.princeton.edu</a>
dc.subject.classificationOrganic chemistry
dc.titleReactivity and Selectivity Controls in Radical Reactions Enabled By Proton-Coupled Electron Transfer
dc.typeAcademic dissertations (Ph.D.)
pu.embargo.terms2023-09-30
pu.date.classyear2022
pu.departmentChemistry
Appears in Collections:Chemistry

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