Nitrogen-containing compounds, specifically the 1,2-oxyamino moiety, are of vital importance to modern pharmaceuticals, natural products, and agrochemicals. 1,2-Difunctionalization of alkenes offers an efficient approach to assemble these scaffolds in a single step from readily available starting materials. In this dissertation, a novel copper-catalyzed amino oxygenation strategy of alkenes has been established using O-benzoylhydroxylamines as an electron-rich amine precursor and oxidant. First, copper-catalyzed amino lactonization was achieved starting with carboxylic acid-tethered alkenes. This intramolecular transformation is also applicable to alcohols, amides, 1,3-diones, oximes, and thioic acids as nucleophilic trapping partners. These reactions proceed in a facile manner, producing good yields and tolerance of a wide range of functional groups with excellent chemo- and regioselectivity. Mechanistic studies explicitly distinguish between a novel, electrophilic amination-initiation event and previously observed nucleophilic oxygenation-initiation events. Furthermore, the procedure can be adapted to carry out the reaction from the free amine as an O-benzoylhydroxylamine precursor. Finally, the intermolecular, three-component amino oxygenation reaction of alkenes was successfully developed using untethered carboxylic acids and O-benzoylhydroxylamines. The analogous three-component amino oxygenation reaction of dienes was also found to proceed effectively in a chemo-, regio-, and site-selective fashion.
","abstract_html":"<p>Nitrogen-containing compounds, specifically the 1,2-oxyamino moiety, are of vital importance to modern pharmaceuticals, natural products, and agrochemicals. 1,2-Difunctionalization of alkenes offers an efficient approach to assemble these scaffolds in a single step from readily available starting materials. In this dissertation, a novel copper-catalyzed amino oxygenation strategy of alkenes has been established using O-benzoylhydroxylamines as an electron-rich amine precursor and oxidant. First, copper-catalyzed amino lactonization was achieved starting with carboxylic acid-tethered alkenes. This intramolecular transformation is also applicable to alcohols, amides, 1,3-diones, oximes, and thioic acids as nucleophilic trapping partners. These reactions proceed in a facile manner, producing good yields and tolerance of a wide range of functional groups with excellent chemo- and regioselectivity. Mechanistic studies explicitly distinguish between a novel, electrophilic amination-initiation event and previously observed nucleophilic oxygenation-initiation events. Furthermore, the procedure can be adapted to carry out the reaction from the free amine as an O-benzoylhydroxylamine precursor. Finally, the intermolecular, three-component amino oxygenation reaction of alkenes was successfully developed using untethered carboxylic acids and O-benzoylhydroxylamines. The analogous three-component amino oxygenation reaction of dienes was also found to proceed effectively in a chemo-, regio-, and site-selective fashion.</p>","abstract_has_math":false,"creators":["Hemric, Brett Nathaniel"],"institution":null,"degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Wang, Qiu"],"committee_chairs":[],"committee_members":[],"year":2018,"date_issued":"2018","date_published":"2018","updated_at":"2026-07-24T02:07:12Z","subjects":["Organic chemistry","alkene","amination","copper"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/10161/18286","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Wang, Qiu"]},{"key":"dc:creator","label":"Author","values":["Hemric, Brett Nathaniel"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2019-04-02T16:27:51Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2021-01-09T09:17:09Z"]},{"key":"dc:date.issued","label":"Date","values":["2018"]},{"key":"dc:type","label":"Dc Type","values":["Dissertation"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Organic chemistry","alkene","amination","copper"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://hdl.handle.net/10161/18286"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Nitrogen-containing compounds, specifically the 1,2-oxyamino moiety, are of vital importance to modern pharmaceuticals, natural products, and agrochemicals. 1,2-Difunctionalization of alkenes offers an efficient approach to assemble these scaffolds in a single step from readily available starting materials. In this dissertation, a novel copper-catalyzed amino oxygenation strategy of alkenes has been established using O-benzoylhydroxylamines as an electron-rich amine precursor and oxidant. First, copper-catalyzed amino lactonization was achieved starting with carboxylic acid-tethered alkenes. This intramolecular transformation is also applicable to alcohols, amides, 1,3-diones, oximes, and thioic acids as nucleophilic trapping partners. These reactions proceed in a facile manner, producing good yields and tolerance of a wide range of functional groups with excellent chemo- and regioselectivity. Mechanistic studies explicitly distinguish between a novel, electrophilic amination-initiation event and previously observed nucleophilic oxygenation-initiation events. Furthermore, the procedure can be adapted to carry out the reaction from the free amine as an O-benzoylhydroxylamine precursor. Finally, the intermolecular, three-component amino oxygenation reaction of alkenes was successfully developed using untethered carboxylic acids and O-benzoylhydroxylamines. The analogous three-component amino oxygenation reaction of dienes was also found to proceed effectively in a chemo-, regio-, and site-selective fashion.
"]},{"key":"dc:title","label":"Title","values":["Copper-Catalyzed Amino Oxygenation of Alkenes and Dienes: A Novel Amino-Initiation Pathway Using O-Benzoylhydroxylamines"]}]}],"canonical_facts":{"dc:contributor.advisor":["Wang, Qiu"],"dc:creator":["Hemric, Brett Nathaniel"],"dc:date.accessioned":["2019-04-02T16:27:51Z"],"dc:date.available":["2021-01-09T09:17:09Z"],"dc:date.issued":["2018"],"dc:description.abstract":["Nitrogen-containing compounds, specifically the 1,2-oxyamino moiety, are of vital importance to modern pharmaceuticals, natural products, and agrochemicals. 1,2-Difunctionalization of alkenes offers an efficient approach to assemble these scaffolds in a single step from readily available starting materials. In this dissertation, a novel copper-catalyzed amino oxygenation strategy of alkenes has been established using O-benzoylhydroxylamines as an electron-rich amine precursor and oxidant. First, copper-catalyzed amino lactonization was achieved starting with carboxylic acid-tethered alkenes. This intramolecular transformation is also applicable to alcohols, amides, 1,3-diones, oximes, and thioic acids as nucleophilic trapping partners. These reactions proceed in a facile manner, producing good yields and tolerance of a wide range of functional groups with excellent chemo- and regioselectivity. Mechanistic studies explicitly distinguish between a novel, electrophilic amination-initiation event and previously observed nucleophilic oxygenation-initiation events. Furthermore, the procedure can be adapted to carry out the reaction from the free amine as an O-benzoylhydroxylamine precursor. Finally, the intermolecular, three-component amino oxygenation reaction of alkenes was successfully developed using untethered carboxylic acids and O-benzoylhydroxylamines. The analogous three-component amino oxygenation reaction of dienes was also found to proceed effectively in a chemo-, regio-, and site-selective fashion.
"],"dc:identifier.uri":["https://hdl.handle.net/10161/18286"],"dc:subject":["Organic chemistry","alkene","amination","copper"],"dc:title":["Copper-Catalyzed Amino Oxygenation of Alkenes and Dienes: A Novel Amino-Initiation Pathway Using O-Benzoylhydroxylamines"],"dc:type":["Dissertation"]},"updated_at":"2026-07-24T02:07:12Z"}