{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/129787"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/129787","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Mechanistic investigations into the origin of chemoselectivity a methylene (csp3) c-h oxidation in the presence of α-β unsaturated carbonyls and exploration of reaction scope","abstract":"Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2027-05-01","abstract_html":"Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2027-05-01","abstract_has_math":false,"creators":["Hartmann, Marc A."],"institution":"University of Illinois Urbana-Champaign","degree_name":"M.S.","degree_level":"Thesis","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["White, M. 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Despite this, methods for (Csp3) C-H to C-O transformations in the presence of this oxidatively sensitive functionality are underexplored and limited exclusively to radical based methods that target the homolytically weak allyic C-H bonds. Recently, our group developed the first method for (Csp3) C-H in the presence of α-β unsaturated carbonyls enabling rapid access to metabolites and analogues of drugs and complex natural products. This thesis documents mechanistic studies designed to uncover the origin of chemoselectivity for strong bond (Csp3) C-H oxidation over epoxidation of the α-β unsaturated carbonyl π system. Through this process, it was discovered that our new Mn(PDP)/HFIP system has a different active oxidant compared to previous our Mn(PDP)/MeCN/ClAcOH system, which is largely responsible for the enhanced chemoselectivity. Additionally, the generality of our method was accessed on both simple and complex α-β unsaturated carbonyl containing compounds."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Mechanistic investigations into the origin of chemoselectivity a methylene (csp3) c-h oxidation in the presence of α-β unsaturated carbonyls and exploration of reaction scope"]}]}],"canonical_facts":{"dc:contributor":["White, M. Christina"],"dc:creator":["Hartmann, Marc A."],"dc:date":["2025-05-08","2025-05"],"dc:description":["Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2027-05-01","The student, Marc Hartmann, accepted the attached license on 2025-05-07 at 22:41.","The student, Marc Hartmann, submitted this Thesis for approval on 2025-05-07 at 22:57.","This Thesis was approved for publication on 2025-05-08 at 17:59.","DSpace SAF Submission Ingestion Package generated from Vireo submission #22263 on 2025-10-19 at 19:55:50","α-β unsaturated carbonyls are a common structural motif in bioactive natural products and pharmaceuticals. Despite this, methods for (Csp3) C-H to C-O transformations in the presence of this oxidatively sensitive functionality are underexplored and limited exclusively to radical based methods that target the homolytically weak allyic C-H bonds. Recently, our group developed the first method for (Csp3) C-H in the presence of α-β unsaturated carbonyls enabling rapid access to metabolites and analogues of drugs and complex natural products. This thesis documents mechanistic studies designed to uncover the origin of chemoselectivity for strong bond (Csp3) C-H oxidation over epoxidation of the α-β unsaturated carbonyl π system. Through this process, it was discovered that our new Mn(PDP)/HFIP system has a different active oxidant compared to previous our Mn(PDP)/MeCN/ClAcOH system, which is largely responsible for the enhanced chemoselectivity. Additionally, the generality of our method was accessed on both simple and complex α-β unsaturated carbonyl containing compounds."],"dc:format":["application/pdf"],"dc:identifier":["https://hdl.handle.net/2142/129787"],"dc:language":["en","eng"],"dc:rights":["Copyright 2025 Marc Hartmann"],"dc:subject":["Catalysis","Methodology","Mechanism"],"dc:title":["Mechanistic investigations into the origin of chemoselectivity a methylene (csp3) c-h oxidation in the presence of α-β unsaturated carbonyls and exploration of reaction scope"],"dc:type":["text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Thesis"],"thesis:degree_name":["M.S."],"thesis:institution_name":["University of Illinois Urbana-Champaign"]},"updated_at":"2026-07-22T22:25:05Z"}