{"id":{"repo_id":"buffalo","oai_identifier":"oai:ubir.buffalo.edu:10477/80648"},"canonical_url":"https://search.dev.ndltd.org/etd/buffalo/oai:ubir.buffalo.edu:10477/80648","repository":{"repo_id":"buffalo","name":"Buffalo","base_url":"https://ubir.buffalo.edu/oai/request"},"display":{"title":"Aerobic Copper-Catalyzed Difunctionalization of Alkenes","abstract":"Ph.D.","abstract_html":"Ph.D.","abstract_has_math":false,"creators":["Wdowik, Tomasz; 0000-0002-9840-1501"],"institution":"State University of New York at Buffalo","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":["Chemler, Sherry","Chemistry"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2019,"date_issued":"2019-10-28T21:17:22Z","date_published":"2019-10-28T21:17:22Z","updated_at":"2026-07-27T19:05:23Z","subjects":["organic chemistry"],"languages":["eng"],"rights":["Users of works found in University at Buffalo Institutional Repository (UBIR) are responsible for identifying and contacting the copyright owner for permission to reuse. University at Buffalo Libraries do not manage rights for copyright-protected works and cannot assist with permissions.","Copyright retained by author."],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/10477/80648","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Chemler, Sherry","Chemistry"]},{"key":"dc:creator","label":"Author","values":["Wdowik, Tomasz; 0000-0002-9840-1501"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2019-10-28T21:17:22Z","2019","2019-08-09 23:23:07"]},{"key":"dc:publisher","label":"Institution","values":["State University of New York at Buffalo"]},{"key":"dc:type","label":"Dc Type","values":["Text","Dissertation"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["organic chemistry"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Users of works found in University at Buffalo Institutional Repository (UBIR) are responsible for identifying and contacting the copyright owner for permission to reuse. University at Buffalo Libraries do not manage rights for copyright-protected works and cannot assist with permissions.","Copyright retained by author."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/10477/80648"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Ph.D.","Oxygen is one of the most important elements, with essential roles in crucial biological and chemical processes. Its high abundance and reactivity make oxygen, in many aspects, an ideal oxidant. Not surprisingly, an exploration of its application in various chemical processes has been the subject of continuous studies, resulting in numerous industrial applications, as well as basic research findings. The use of molecular oxygen in catalysis constitutes a particularly interesting area of research from a practical point of view as it addresses issues of sustainability and atom economy. This is especially true for catalytic systems based on more abundant first-row transition metals, such as copper. This thesis presents research that fits into these trends and discusses the use of molecular oxygen in copper-catalyzed difunctionalizations of alkenes. Chapter 1 focuses on transforming copper-catalyzed alkene difunctionalization protocols from one that utilizes manganese dioxide as an oxidant into an aerobic transformation. This was particularly explored for intramolecular carboaminations and carboetherifications of terminal alkenes. In addition, the potential of this approach for intermolecular reactions was also explored. Successful optimization enabled achievement of high enantioselectivity of intramolecular reactions. Further, the use of 10% of oxygen in nitrogen was found to be effective in this reaction, indicating the potential of these reactions on a larger scale, where concerns about using oxygen in the presence of flammable organic solvents cannot be neglected. Chapter 2 presents studies on oxygen acting as a reagent and an oxidant in copper-catalyzed difunctionalization of alkenes. This new methodology enables access to heterocyclic aldehydes that can be isolated or can undergo further oxidative carbon–carbon bond cleavage, resulting in the formation of gamma-lactams and gamma-lactones. The utility of this method was demonstrated on formal syntheses of biologically active compounds. These findings were supplemented by mechanistic studies as well as explorations of the asymmetric aspect of an aldehyde formation. Additionally, preliminary studies on the oxidation of benzylic radical resulting from hydrogen atom transfer to primary radical were discussed."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Aerobic Copper-Catalyzed Difunctionalization of Alkenes"]}]}],"canonical_facts":{"dc:contributor":["Chemler, Sherry","Chemistry"],"dc:creator":["Wdowik, Tomasz; 0000-0002-9840-1501"],"dc:date":["2019-10-28T21:17:22Z","2019","2019-08-09 23:23:07"],"dc:description":["Ph.D.","Oxygen is one of the most important elements, with essential roles in crucial biological and chemical processes. Its high abundance and reactivity make oxygen, in many aspects, an ideal oxidant. Not surprisingly, an exploration of its application in various chemical processes has been the subject of continuous studies, resulting in numerous industrial applications, as well as basic research findings. The use of molecular oxygen in catalysis constitutes a particularly interesting area of research from a practical point of view as it addresses issues of sustainability and atom economy. This is especially true for catalytic systems based on more abundant first-row transition metals, such as copper. This thesis presents research that fits into these trends and discusses the use of molecular oxygen in copper-catalyzed difunctionalizations of alkenes. Chapter 1 focuses on transforming copper-catalyzed alkene difunctionalization protocols from one that utilizes manganese dioxide as an oxidant into an aerobic transformation. This was particularly explored for intramolecular carboaminations and carboetherifications of terminal alkenes. In addition, the potential of this approach for intermolecular reactions was also explored. Successful optimization enabled achievement of high enantioselectivity of intramolecular reactions. Further, the use of 10% of oxygen in nitrogen was found to be effective in this reaction, indicating the potential of these reactions on a larger scale, where concerns about using oxygen in the presence of flammable organic solvents cannot be neglected. Chapter 2 presents studies on oxygen acting as a reagent and an oxidant in copper-catalyzed difunctionalization of alkenes. This new methodology enables access to heterocyclic aldehydes that can be isolated or can undergo further oxidative carbon–carbon bond cleavage, resulting in the formation of gamma-lactams and gamma-lactones. The utility of this method was demonstrated on formal syntheses of biologically active compounds. These findings were supplemented by mechanistic studies as well as explorations of the asymmetric aspect of an aldehyde formation. Additionally, preliminary studies on the oxidation of benzylic radical resulting from hydrogen atom transfer to primary radical were discussed."],"dc:format":["application/pdf"],"dc:identifier":["http://hdl.handle.net/10477/80648"],"dc:language":["eng"],"dc:publisher":["State University of New York at Buffalo"],"dc:rights":["Users of works found in University at Buffalo Institutional Repository (UBIR) are responsible for identifying and contacting the copyright owner for permission to reuse. University at Buffalo Libraries do not manage rights for copyright-protected works and cannot assist with permissions.","Copyright retained by author."],"dc:subject":["organic chemistry"],"dc:title":["Aerobic Copper-Catalyzed Difunctionalization of Alkenes"],"dc:type":["Text","Dissertation"]},"updated_at":"2026-07-27T19:05:23Z"}