{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/99462"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/99462","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Hydroamination of terminal allylic imines, allylic amines, and internal and terminal homoallylic amines: Regioselective and regiodivergent transformations","abstract":"C–N bonds are ubiquitous in organic chemistry. Mild methods that allow for the direct formation of this motif from readily accessible functional groups would represent a powerful advance in organic synthesis. The intermolecular hydroamination of alkenes and amines represents a novel approach towards these disconnections from readily accessible functional groups. This transformation can streamline the synthesis of complex molecules and often allows access to two regioisomers (Markovnikov and anti-Markovnikov) from one starting material. 1,2-diamines are a common motif in many organic molecules. However, their synthesis often involves a lengthy, multi-step synthetic sequence. We report the Rh- and Ir-catalyzed addition of secondary cyclic, secondary acyclic, and primary acyclic (both aryl and aliphatic) amines to allyl amine. This transformation is highly chemoselective, regioselective, functional group tolerant, and can be used to form trans-diamines with excellent selectivity. Future directions for this method, including anti-Markovnikov and/or asymmetric hydroamination are discussed. The anti-Markovnikov hydroamination of aliphatic alkenes is a significant challenge for organometallic chemists. These products are typically formed via formal hydroamination. We report the Rh-catalyzed anti-Markovnikov selective hydroamination of homoallylic amines to form 1,4-diamines with electron rich secondary cyclic and acyclic amine nucleophiles. This transformation is tolerant of a variety of substituents on the homoallylic amine and mechanistic studies on these substrates are summarized. The regiodivergent functionalization of a substrate is a powerful method in organic chemistry; in the hydroamination literature, this transformation typically requires activated alkenes (allenes, dienes, etc.) and is limited in scope. The regiodivergent intermolecular hydroamination of homoallylic amines to selectively form either 1,3- or 1,4-diamines is disclosed. This method features both novel aryl amine nucleophiles and catalysts to form the desired product. This transformation is demonstrated on both terminal and internal alkenes and future directions are proposed.","abstract_html":"C–N bonds are ubiquitous in organic chemistry. Mild methods that allow for the direct formation of this motif from readily accessible functional groups would represent a powerful advance in organic synthesis. The intermolecular hydroamination of alkenes and amines represents a novel approach towards these disconnections from readily accessible functional groups. This transformation can streamline the synthesis of complex molecules and often allows access to two regioisomers (Markovnikov and anti-Markovnikov) from one starting material. 1,2-diamines are a common motif in many organic molecules. However, their synthesis often involves a lengthy, multi-step synthetic sequence. We report the Rh- and Ir-catalyzed addition of secondary cyclic, secondary acyclic, and primary acyclic (both aryl and aliphatic) amines to allyl amine. This transformation is highly chemoselective, regioselective, functional group tolerant, and can be used to form trans-diamines with excellent selectivity. Future directions for this method, including anti-Markovnikov and/or asymmetric hydroamination are discussed. The anti-Markovnikov hydroamination of aliphatic alkenes is a significant challenge for organometallic chemists. These products are typically formed via formal hydroamination. We report the Rh-catalyzed anti-Markovnikov selective hydroamination of homoallylic amines to form 1,4-diamines with electron rich secondary cyclic and acyclic amine nucleophiles. This transformation is tolerant of a variety of substituents on the homoallylic amine and mechanistic studies on these substrates are summarized. The regiodivergent functionalization of a substrate is a powerful method in organic chemistry; in the hydroamination literature, this transformation typically requires activated alkenes (allenes, dienes, etc.) and is limited in scope. The regiodivergent intermolecular hydroamination of homoallylic amines to selectively form either 1,3- or 1,4-diamines is disclosed. This method features both novel aryl amine nucleophiles and catalysts to form the desired product. This transformation is demonstrated on both terminal and internal alkenes and future directions are proposed.","abstract_has_math":false,"creators":["Ensign, Seth Cody"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Hull, Kami L.","Fout, Alison R.","Moore, Jeffrey S.","White, M. Christina"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2018,"date_issued":"2018-03-13T17:29:02Z","date_published":"2018-03-13T17:29:02Z","updated_at":"2026-07-22T22:24:37Z","subjects":["Hydroamination","Rhodium","Iridium","Allylic amines","Allylic imines","Homoallylic amines"],"languages":["en"],"rights":["Copyright 2017 Seth Ensign"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/99462","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Hull, Kami L.","Fout, Alison R.","Moore, Jeffrey S.","White, M. Christina"]},{"key":"dc:creator","label":"Author","values":["Ensign, Seth Cody"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2018-03-13T17:29:02Z","2020-03-14T09:15:16Z","2017-09-14","2017-12"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois at Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Hydroamination","Rhodium","Iridium","Allylic amines","Allylic imines","Homoallylic amines"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2017 Seth Ensign"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/99462"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["C–N bonds are ubiquitous in organic chemistry. Mild methods that allow for the direct formation of this motif from readily accessible functional groups would represent a powerful advance in organic synthesis. The intermolecular hydroamination of alkenes and amines represents a novel approach towards these disconnections from readily accessible functional groups. This transformation can streamline the synthesis of complex molecules and often allows access to two regioisomers (Markovnikov and anti-Markovnikov) from one starting material. 1,2-diamines are a common motif in many organic molecules. However, their synthesis often involves a lengthy, multi-step synthetic sequence. We report the Rh- and Ir-catalyzed addition of secondary cyclic, secondary acyclic, and primary acyclic (both aryl and aliphatic) amines to allyl amine. This transformation is highly chemoselective, regioselective, functional group tolerant, and can be used to form trans-diamines with excellent selectivity. Future directions for this method, including anti-Markovnikov and/or asymmetric hydroamination are discussed. The anti-Markovnikov hydroamination of aliphatic alkenes is a significant challenge for organometallic chemists. These products are typically formed via formal hydroamination. We report the Rh-catalyzed anti-Markovnikov selective hydroamination of homoallylic amines to form 1,4-diamines with electron rich secondary cyclic and acyclic amine nucleophiles. This transformation is tolerant of a variety of substituents on the homoallylic amine and mechanistic studies on these substrates are summarized. The regiodivergent functionalization of a substrate is a powerful method in organic chemistry; in the hydroamination literature, this transformation typically requires activated alkenes (allenes, dienes, etc.) and is limited in scope. The regiodivergent intermolecular hydroamination of homoallylic amines to selectively form either 1,3- or 1,4-diamines is disclosed. This method features both novel aryl amine nucleophiles and catalysts to form the desired product. This transformation is demonstrated on both terminal and internal alkenes and future directions are proposed.","Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2019-12-01","The student, Seth Ensign, accepted the attached license on 2017-09-01 at 07:03.","The student, Seth Ensign, submitted this Dissertation for approval on 2017-09-01 at 07:07.","This Dissertation was approved for publication on 2017-09-14 at 13:12.","DSpace SAF Submission Ingestion Package generated from Vireo submission #11629 on 2018-03-13 at 10:32:34","Made available in DSpace on 2018-03-13T17:29:02Z (GMT). No. of bitstreams: 5 ENSIGN-DISSERTATION-2017.pdf: 6723665 bytes, checksum: 392709dc75ca69c839da00cc35777a63 (MD5) Ensign 2015 Permission.pdf: 137739 bytes, checksum: 591eeca4b097ef73ec00843441383f19 (MD5) Ickes 2014 Permission.pdf: 137119 bytes, checksum: 273521ff9b9772d7a6d58528c6636290 (MD5) LICENSE.txt: 4208 bytes, checksum: 23c234e7409f1d4a5ec5948dafebd4e1 (MD5) PROQUEST_LICENSE.txt: 4554 bytes, checksum: 92b1195db74ee11e82be870e0ca49732 (MD5) Previous issue date: 2017-09-14","Embargo set by: Seth Robbins for item 105429 Lift date: 2020-03-13T17:29:20Z Reason: Author requested closed access (OA after 2yrs) in Vireo ETD system","Embargo set by: Seth Robbins for item 105429 Lift date: 2020-03-13T17:32:30Z Reason: Author requested closed access (OA after 2yrs) in Vireo ETD system","Embargo set by: Seth Robbins for item 105429 Lift date: 2020-03-13T17:36:05Z Reason: Author requested closed access (OA after 2yrs) in Vireo ETD system","Limited Restriction Lifted for Item 105429 on 2020-03-14T09:15:16Z."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Hydroamination of terminal allylic imines, allylic amines, and internal and terminal homoallylic amines: Regioselective and regiodivergent transformations"]}]}],"canonical_facts":{"dc:contributor":["Hull, Kami L.","Fout, Alison R.","Moore, Jeffrey S.","White, M. Christina"],"dc:creator":["Ensign, Seth Cody"],"dc:date":["2018-03-13T17:29:02Z","2020-03-14T09:15:16Z","2017-09-14","2017-12"],"dc:description":["C–N bonds are ubiquitous in organic chemistry. Mild methods that allow for the direct formation of this motif from readily accessible functional groups would represent a powerful advance in organic synthesis. The intermolecular hydroamination of alkenes and amines represents a novel approach towards these disconnections from readily accessible functional groups. This transformation can streamline the synthesis of complex molecules and often allows access to two regioisomers (Markovnikov and anti-Markovnikov) from one starting material. 1,2-diamines are a common motif in many organic molecules. However, their synthesis often involves a lengthy, multi-step synthetic sequence. We report the Rh- and Ir-catalyzed addition of secondary cyclic, secondary acyclic, and primary acyclic (both aryl and aliphatic) amines to allyl amine. This transformation is highly chemoselective, regioselective, functional group tolerant, and can be used to form trans-diamines with excellent selectivity. Future directions for this method, including anti-Markovnikov and/or asymmetric hydroamination are discussed. The anti-Markovnikov hydroamination of aliphatic alkenes is a significant challenge for organometallic chemists. These products are typically formed via formal hydroamination. We report the Rh-catalyzed anti-Markovnikov selective hydroamination of homoallylic amines to form 1,4-diamines with electron rich secondary cyclic and acyclic amine nucleophiles. This transformation is tolerant of a variety of substituents on the homoallylic amine and mechanistic studies on these substrates are summarized. The regiodivergent functionalization of a substrate is a powerful method in organic chemistry; in the hydroamination literature, this transformation typically requires activated alkenes (allenes, dienes, etc.) and is limited in scope. The regiodivergent intermolecular hydroamination of homoallylic amines to selectively form either 1,3- or 1,4-diamines is disclosed. This method features both novel aryl amine nucleophiles and catalysts to form the desired product. This transformation is demonstrated on both terminal and internal alkenes and future directions are proposed.","Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2019-12-01","The student, Seth Ensign, accepted the attached license on 2017-09-01 at 07:03.","The student, Seth Ensign, submitted this Dissertation for approval on 2017-09-01 at 07:07.","This Dissertation was approved for publication on 2017-09-14 at 13:12.","DSpace SAF Submission Ingestion Package generated from Vireo submission #11629 on 2018-03-13 at 10:32:34","Made available in DSpace on 2018-03-13T17:29:02Z (GMT). No. of bitstreams: 5 ENSIGN-DISSERTATION-2017.pdf: 6723665 bytes, checksum: 392709dc75ca69c839da00cc35777a63 (MD5) Ensign 2015 Permission.pdf: 137739 bytes, checksum: 591eeca4b097ef73ec00843441383f19 (MD5) Ickes 2014 Permission.pdf: 137119 bytes, checksum: 273521ff9b9772d7a6d58528c6636290 (MD5) LICENSE.txt: 4208 bytes, checksum: 23c234e7409f1d4a5ec5948dafebd4e1 (MD5) PROQUEST_LICENSE.txt: 4554 bytes, checksum: 92b1195db74ee11e82be870e0ca49732 (MD5) Previous issue date: 2017-09-14","Embargo set by: Seth Robbins for item 105429 Lift date: 2020-03-13T17:29:20Z Reason: Author requested closed access (OA after 2yrs) in Vireo ETD system","Embargo set by: Seth Robbins for item 105429 Lift date: 2020-03-13T17:32:30Z Reason: Author requested closed access (OA after 2yrs) in Vireo ETD system","Embargo set by: Seth Robbins for item 105429 Lift date: 2020-03-13T17:36:05Z Reason: Author requested closed access (OA after 2yrs) in Vireo ETD system","Limited Restriction Lifted for Item 105429 on 2020-03-14T09:15:16Z."],"dc:format":["application/pdf"],"dc:identifier":["http://hdl.handle.net/2142/99462"],"dc:language":["en"],"dc:rights":["Copyright 2017 Seth Ensign"],"dc:subject":["Hydroamination","Rhodium","Iridium","Allylic amines","Allylic imines","Homoallylic amines"],"dc:title":["Hydroamination of terminal allylic imines, allylic amines, and internal and terminal homoallylic amines: Regioselective and regiodivergent transformations"],"dc:type":["text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:24:37Z"}