{"id":{"repo_id":"ku","oai_identifier":"oai:kuscholarworks.ku.edu:1808/37257"},"canonical_url":"https://search.dev.ndltd.org/etd/ku/oai:kuscholarworks.ku.edu:1808/37257","repository":{"repo_id":"ku","name":"University of Kansas","base_url":"https://kuscholarworks.ku.edu/server/oai/request"},"display":{"title":"Quinone-Catalyzed Amine α-C–H and α-C–C Functionalization","abstract":"Amines are extremely useful compounds with diverse applications in multiple disciplines. For this reason, a myriad of synthetic methods has been developed for the preparation of amine compounds. Despite this, the majority of well-established methodology for amine synthesis relies on the introduction of amino groups. Emerging amine α-functionalization methodology enables the modification of existing amine-containing molecules at the α-amino position therefore providing new approaches to amine synthesis. Driven by our research interest in amine synthesis, we set out to explore novel synthetic methods for organocatalytic α-C–H functionalization of amine-containing molecules. Inspired by enzymatic catalysis, we studied sequential quinone-catalyzed oxidation/nucleophilic addition reactions of primary aromatic amines to quickly access corresponding α-substituted amines. The developed reaction conditions can be effectively applied to gram-scale synthesis. The excellent reactivity of quinone in oxidative amine C–H functionalization motived to us to investigate quinone-catalyzed oxidative C–C functionalization of amine-containing molecules. In this regard, we developed a novel method for homologation of aromatic α-amino acids through sequential quinone-catalyzed oxidative decarboxylation/Mukaiyama−Mannich addition under mild reaction conditions. Following this discovery, quinone-catalyzed deformylative functionalization of aromatic β-amino alcohols was realized to further demonstrate the synthetic utility of quinone-catalyzed oxidative C–C functionalization. Lastly, we addressed the scope limitation of quinone-catalyzed oxidative α-functionalization of amine-containing molecules. Through systematic optimization process, suitable conditions to incorporate aliphatic substrates were discovered. Hitherto we have developed a general methodology for quinone-catalyzed α-functionalization of amine-containing molecules. Taken together, these methods are expected to be useful for efficient amine synthesis and late-stage functionalization of natural products and drug molecules.","abstract_html":"Amines are extremely useful compounds with diverse applications in multiple disciplines. For this reason, a myriad of synthetic methods has been developed for the preparation of amine compounds. Despite this, the majority of well-established methodology for amine synthesis relies on the introduction of amino groups. Emerging amine α-functionalization methodology enables the modification of existing amine-containing molecules at the α-amino position therefore providing new approaches to amine synthesis. Driven by our research interest in amine synthesis, we set out to explore novel synthetic methods for organocatalytic α-C–H functionalization of amine-containing molecules. Inspired by enzymatic catalysis, we studied sequential quinone-catalyzed oxidation/nucleophilic addition reactions of primary aromatic amines to quickly access corresponding α-substituted amines. The developed reaction conditions can be effectively applied to gram-scale synthesis. The excellent reactivity of quinone in oxidative amine C–H functionalization motived to us to investigate quinone-catalyzed oxidative C–C functionalization of amine-containing molecules. In this regard, we developed a novel method for homologation of aromatic α-amino acids through sequential quinone-catalyzed oxidative decarboxylation/Mukaiyama−Mannich addition under mild reaction conditions. Following this discovery, quinone-catalyzed deformylative functionalization of aromatic β-amino alcohols was realized to further demonstrate the synthetic utility of quinone-catalyzed oxidative C–C functionalization. Lastly, we addressed the scope limitation of quinone-catalyzed oxidative α-functionalization of amine-containing molecules. Through systematic optimization process, suitable conditions to incorporate aliphatic substrates were discovered. Hitherto we have developed a general methodology for quinone-catalyzed α-functionalization of amine-containing molecules. Taken together, these methods are expected to be useful for efficient amine synthesis and late-stage functionalization of natural products and drug molecules.","abstract_has_math":false,"creators":["Liu, Xinyun"],"institution":"University of Kansas","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Clift, Michael D"],"committee_chairs":[],"committee_members":[],"year":2018,"date_issued":"2018-01-01","date_published":"2018-01-01","updated_at":"2026-07-24T02:45:54Z","subjects":["Organic chemistry","amine synthesis","amine α-functionalization","organocatalysis","quinone catalysis"],"languages":["en"],"rights":["Copyright held by the author."],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier.other","label":"Dc Identifier Other","values":["http://dissertations.umi.com/ku:16145"],"render_values":[{"text":"http://dissertations.umi.com/ku:16145","href":"http://dissertations.umi.com/ku:16145","code":true}]}]},"links":{"outbound_url":"https://hdl.handle.net/1808/37257","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Clift, Michael D"]},{"key":"dc:creator","label":"Author","values":["Liu, Xinyun"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2026-04-14T19:00:33Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2026-04-14T19:00:33Z"]},{"key":"dc:date.issued","label":"Date","values":["2018-01-01"]},{"key":"dc:publisher","label":"Institution","values":["University of Kansas"]},{"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","amine synthesis","amine α-functionalization","organocatalysis","quinone catalysis"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright held by the author."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.other","label":"Dc Identifier Other","values":["http://dissertations.umi.com/ku:16145"]},{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://hdl.handle.net/1808/37257"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Amines are extremely useful compounds with diverse applications in multiple disciplines. For this reason, a myriad of synthetic methods has been developed for the preparation of amine compounds. Despite this, the majority of well-established methodology for amine synthesis relies on the introduction of amino groups. Emerging amine α-functionalization methodology enables the modification of existing amine-containing molecules at the α-amino position therefore providing new approaches to amine synthesis. Driven by our research interest in amine synthesis, we set out to explore novel synthetic methods for organocatalytic α-C–H functionalization of amine-containing molecules. Inspired by enzymatic catalysis, we studied sequential quinone-catalyzed oxidation/nucleophilic addition reactions of primary aromatic amines to quickly access corresponding α-substituted amines. The developed reaction conditions can be effectively applied to gram-scale synthesis. The excellent reactivity of quinone in oxidative amine C–H functionalization motived to us to investigate quinone-catalyzed oxidative C–C functionalization of amine-containing molecules. In this regard, we developed a novel method for homologation of aromatic α-amino acids through sequential quinone-catalyzed oxidative decarboxylation/Mukaiyama−Mannich addition under mild reaction conditions. Following this discovery, quinone-catalyzed deformylative functionalization of aromatic β-amino alcohols was realized to further demonstrate the synthetic utility of quinone-catalyzed oxidative C–C functionalization. Lastly, we addressed the scope limitation of quinone-catalyzed oxidative α-functionalization of amine-containing molecules. Through systematic optimization process, suitable conditions to incorporate aliphatic substrates were discovered. Hitherto we have developed a general methodology for quinone-catalyzed α-functionalization of amine-containing molecules. Taken together, these methods are expected to be useful for efficient amine synthesis and late-stage functionalization of natural products and drug molecules."]},{"key":"dc:title","label":"Title","values":["Quinone-Catalyzed Amine α-C–H and α-C–C Functionalization"]}]}],"canonical_facts":{"dc:contributor.advisor":["Clift, Michael D"],"dc:creator":["Liu, Xinyun"],"dc:date.accessioned":["2026-04-14T19:00:33Z"],"dc:date.available":["2026-04-14T19:00:33Z"],"dc:date.issued":["2018-01-01"],"dc:description.abstract":["Amines are extremely useful compounds with diverse applications in multiple disciplines. For this reason, a myriad of synthetic methods has been developed for the preparation of amine compounds. Despite this, the majority of well-established methodology for amine synthesis relies on the introduction of amino groups. Emerging amine α-functionalization methodology enables the modification of existing amine-containing molecules at the α-amino position therefore providing new approaches to amine synthesis. Driven by our research interest in amine synthesis, we set out to explore novel synthetic methods for organocatalytic α-C–H functionalization of amine-containing molecules. Inspired by enzymatic catalysis, we studied sequential quinone-catalyzed oxidation/nucleophilic addition reactions of primary aromatic amines to quickly access corresponding α-substituted amines. The developed reaction conditions can be effectively applied to gram-scale synthesis. The excellent reactivity of quinone in oxidative amine C–H functionalization motived to us to investigate quinone-catalyzed oxidative C–C functionalization of amine-containing molecules. In this regard, we developed a novel method for homologation of aromatic α-amino acids through sequential quinone-catalyzed oxidative decarboxylation/Mukaiyama−Mannich addition under mild reaction conditions. Following this discovery, quinone-catalyzed deformylative functionalization of aromatic β-amino alcohols was realized to further demonstrate the synthetic utility of quinone-catalyzed oxidative C–C functionalization. Lastly, we addressed the scope limitation of quinone-catalyzed oxidative α-functionalization of amine-containing molecules. Through systematic optimization process, suitable conditions to incorporate aliphatic substrates were discovered. Hitherto we have developed a general methodology for quinone-catalyzed α-functionalization of amine-containing molecules. Taken together, these methods are expected to be useful for efficient amine synthesis and late-stage functionalization of natural products and drug molecules."],"dc:identifier.other":["http://dissertations.umi.com/ku:16145"],"dc:identifier.uri":["https://hdl.handle.net/1808/37257"],"dc:language.iso":["en"],"dc:publisher":["University of Kansas"],"dc:rights":["Copyright held by the author."],"dc:subject":["Organic chemistry","amine synthesis","amine α-functionalization","organocatalysis","quinone catalysis"],"dc:title":["Quinone-Catalyzed Amine α-C–H and α-C–C Functionalization"],"dc:type":["Dissertation"]},"updated_at":"2026-07-24T02:45:54Z"}