{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/95581"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/95581","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Transition metal-catalyzed olefin functionalization for highly regio-, enantio-, and chemoselective C–X bond formation","abstract":"The development of alkene functionalizations is an important challenge in modern catalysis.1 This thesis specifically focuses on using transition metal-catalysis to form C–X bonds from C–C double bonds with high degrees of regio-, chemo-, and stereoselectivity. In chapter 1, a regiodivergent Rh-catalyzed hydrothiolation of allyl amines to form 1,2- or 1,3-aminothioethers with excellent degrees of regioselectivity is reported. Bidentate phosphine ligands with larger natural bite angles (βn ≥ 99°) promote a Markovnikov-selective hydrothiolation in up to 88% yield and >20:1 regioselectivity. Conversely, when smaller bite angle ligands (βn ≤ 86°), are employed, the anti-Markovnikov product is formed in up to 74% yield and >20:1 regioselectivity. Initial mechanistic investigations are consistent with an oxidative addition/olefin insertion/reductive elimination mechanism for each pathway. We hypothesize that the change in regioselectivity is an effect of diverging coordination spheres to favor either Rh–S or Rh–H insertion to form the branched or linear isomer, respectively. In chapter 2, initial studies on an asymmetric hydroamination method for the highly enantioselective formation of a chiral 1,2-diamine are discussed. To our delight, we have identified a MeO-BIPHEP-type ligand that promotes the hydroamination of allyl amines in moderate yield with excellent enantioselectivity. Ligand discovery and initial optimization are described. Finally, in chapter 3, an anti-Markovnikov oxidative amination reaction of terminal olefins with pendent aryl- or alcohol functionality is presented. Alkenes are shown to react with imides in the presence of a palladate catalyst to afford the terminally aminated product. Following an anti-Markovnikov selective trans-aminopalladation, a thermodynamically-driven redox relay process occurs away from the newly formed C–N bond to afford a terminal Csp3–N bond and a ketone or styrene moiety. The functional group tolerance is explored and results of preliminary mechanistic investigations are shown.","abstract_html":"The development of alkene functionalizations is an important challenge in modern catalysis.1 This thesis specifically focuses on using transition metal-catalysis to form C–X bonds from C–C double bonds with high degrees of regio-, chemo-, and stereoselectivity. In chapter 1, a regiodivergent Rh-catalyzed hydrothiolation of allyl amines to form 1,2- or 1,3-aminothioethers with excellent degrees of regioselectivity is reported. Bidentate phosphine ligands with larger natural bite angles (βn ≥ 99°) promote a Markovnikov-selective hydrothiolation in up to 88% yield and >20:1 regioselectivity. Conversely, when smaller bite angle ligands (βn ≤ 86°), are employed, the anti-Markovnikov product is formed in up to 74% yield and >20:1 regioselectivity. Initial mechanistic investigations are consistent with an oxidative addition/olefin insertion/reductive elimination mechanism for each pathway. We hypothesize that the change in regioselectivity is an effect of diverging coordination spheres to favor either Rh–S or Rh–H insertion to form the branched or linear isomer, respectively. In chapter 2, initial studies on an asymmetric hydroamination method for the highly enantioselective formation of a chiral 1,2-diamine are discussed. To our delight, we have identified a MeO-BIPHEP-type ligand that promotes the hydroamination of allyl amines in moderate yield with excellent enantioselectivity. Ligand discovery and initial optimization are described. Finally, in chapter 3, an anti-Markovnikov oxidative amination reaction of terminal olefins with pendent aryl- or alcohol functionality is presented. Alkenes are shown to react with imides in the presence of a palladate catalyst to afford the terminally aminated product. Following an anti-Markovnikov selective trans-aminopalladation, a thermodynamically-driven redox relay process occurs away from the newly formed C–N bond to afford a terminal Csp3–N bond and a ketone or styrene moiety. The functional group tolerance is explored and results of preliminary mechanistic investigations are shown.","abstract_has_math":false,"creators":["Kennemur, Jennifer L"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"M.S.","degree_level":"Thesis","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Hull, Kami L.","Rauchfuss, Thomas B.","White, M. Christina","van der Donk, Wilfred"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2017,"date_issued":"2017-03-01T17:01:28Z","date_published":"2017-03-01T17:01:28Z","updated_at":"2026-07-22T22:26:37Z","subjects":["olefin functionalization","rhodium-catalysis","hydrothiolation","hydroamination","oxidative amination."],"languages":["en"],"rights":["Copyright 2016 Jennifer Kennemur"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/95581","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Hull, Kami L.","Rauchfuss, Thomas B.","White, M. 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In chapter 1, a regiodivergent Rh-catalyzed hydrothiolation of allyl amines to form 1,2- or 1,3-aminothioethers with excellent degrees of regioselectivity is reported. Bidentate phosphine ligands with larger natural bite angles (βn ≥ 99°) promote a Markovnikov-selective hydrothiolation in up to 88% yield and >20:1 regioselectivity. Conversely, when smaller bite angle ligands (βn ≤ 86°), are employed, the anti-Markovnikov product is formed in up to 74% yield and >20:1 regioselectivity. Initial mechanistic investigations are consistent with an oxidative addition/olefin insertion/reductive elimination mechanism for each pathway. We hypothesize that the change in regioselectivity is an effect of diverging coordination spheres to favor either Rh–S or Rh–H insertion to form the branched or linear isomer, respectively. In chapter 2, initial studies on an asymmetric hydroamination method for the highly enantioselective formation of a chiral 1,2-diamine are discussed. To our delight, we have identified a MeO-BIPHEP-type ligand that promotes the hydroamination of allyl amines in moderate yield with excellent enantioselectivity. Ligand discovery and initial optimization are described. Finally, in chapter 3, an anti-Markovnikov oxidative amination reaction of terminal olefins with pendent aryl- or alcohol functionality is presented. Alkenes are shown to react with imides in the presence of a palladate catalyst to afford the terminally aminated product. Following an anti-Markovnikov selective trans-aminopalladation, a thermodynamically-driven redox relay process occurs away from the newly formed C–N bond to afford a terminal Csp3–N bond and a ketone or styrene moiety. The functional group tolerance is explored and results of preliminary mechanistic investigations are shown.","Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2018-12-01","The student, Jennifer Kennemur, accepted the attached license on 2016-11-21 at 15:18.","The student, Jennifer Kennemur, submitted this Thesis for approval on 2016-11-21 at 15:25.","This Thesis was approved for publication on 2016-11-23 at 09:54.","DSpace SAF Submission Ingestion Package generated from Vireo submission #10289 on 2017-02-28 at 14:41:55","Made available in DSpace on 2017-03-01T17:01:28Z (GMT). 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Christina","van der Donk, Wilfred"],"dc:creator":["Kennemur, Jennifer L"],"dc:date":["2017-03-01T17:01:28Z","2019-03-02T10:15:27Z","2016-11-23","2016-12"],"dc:description":["The development of alkene functionalizations is an important challenge in modern catalysis.1 This thesis specifically focuses on using transition metal-catalysis to form C–X bonds from C–C double bonds with high degrees of regio-, chemo-, and stereoselectivity. In chapter 1, a regiodivergent Rh-catalyzed hydrothiolation of allyl amines to form 1,2- or 1,3-aminothioethers with excellent degrees of regioselectivity is reported. Bidentate phosphine ligands with larger natural bite angles (βn ≥ 99°) promote a Markovnikov-selective hydrothiolation in up to 88% yield and >20:1 regioselectivity. Conversely, when smaller bite angle ligands (βn ≤ 86°), are employed, the anti-Markovnikov product is formed in up to 74% yield and >20:1 regioselectivity. Initial mechanistic investigations are consistent with an oxidative addition/olefin insertion/reductive elimination mechanism for each pathway. We hypothesize that the change in regioselectivity is an effect of diverging coordination spheres to favor either Rh–S or Rh–H insertion to form the branched or linear isomer, respectively. In chapter 2, initial studies on an asymmetric hydroamination method for the highly enantioselective formation of a chiral 1,2-diamine are discussed. To our delight, we have identified a MeO-BIPHEP-type ligand that promotes the hydroamination of allyl amines in moderate yield with excellent enantioselectivity. Ligand discovery and initial optimization are described. Finally, in chapter 3, an anti-Markovnikov oxidative amination reaction of terminal olefins with pendent aryl- or alcohol functionality is presented. Alkenes are shown to react with imides in the presence of a palladate catalyst to afford the terminally aminated product. Following an anti-Markovnikov selective trans-aminopalladation, a thermodynamically-driven redox relay process occurs away from the newly formed C–N bond to afford a terminal Csp3–N bond and a ketone or styrene moiety. The functional group tolerance is explored and results of preliminary mechanistic investigations are shown.","Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2018-12-01","The student, Jennifer Kennemur, accepted the attached license on 2016-11-21 at 15:18.","The student, Jennifer Kennemur, submitted this Thesis for approval on 2016-11-21 at 15:25.","This Thesis was approved for publication on 2016-11-23 at 09:54.","DSpace SAF Submission Ingestion Package generated from Vireo submission #10289 on 2017-02-28 at 14:41:55","Made available in DSpace on 2017-03-01T17:01:28Z (GMT). No. of bitstreams: 2 KENNEMUR-THESIS-2016.pdf: 9855893 bytes, checksum: f0648f32a6af394381d439833195f34a (MD5) LICENSE.txt: 4214 bytes, checksum: c5a48c392c065a11b3fc336731ff628b (MD5) Previous issue date: 2016-11-23","Embargo set by: Seth Robbins for item 98697 Lift date: 2019-03-01T17:02:22Z Reason: Author requested closed access (OA after 2yrs) in Vireo ETD system","Embargo set by: Seth Robbins for item 98697 Lift date: 2019-03-01T17:03:32Z Reason: Author requested closed access (OA after 2yrs) in Vireo ETD system","Embargo set by: Seth Robbins for item 98697 Lift date: 2019-03-01T17:05:02Z Reason: Author requested closed access (OA after 2yrs) in Vireo ETD system","Embargo set by: Seth Robbins for item 98697 Lift date: 2019-03-01T17:06:55Z Reason: Author requested closed access (OA after 2yrs) in Vireo ETD system","Limited Restriction Lifted for Item 98697 on 2019-03-02T10:15:27Z."],"dc:format":["application/pdf"],"dc:identifier":["http://hdl.handle.net/2142/95581"],"dc:language":["en"],"dc:rights":["Copyright 2016 Jennifer Kennemur"],"dc:subject":["olefin functionalization","rhodium-catalysis","hydrothiolation","hydroamination","oxidative amination."],"dc:title":["Transition metal-catalyzed olefin functionalization for highly regio-, enantio-, and chemoselective C–X bond formation"],"dc:type":["text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Thesis"],"thesis:degree_name":["M.S."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:26:37Z"}