{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/95603"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/95603","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"The development of a rhodium-catalyzed chemo- and stereoselective hydroamination for the synthesis of 1,2-diamines","abstract":"Amines are a prominent functionality found throughout organic molecules, including pharmaceuticals, agrochemicals, organic materials, and organic dyes.1 However, incorporation of amines into organic frameworks in step and atom economical fashion remains a significant challenge to synthetic chemists.2–4 In chapter 1, the importance of a class of compounds, 1,2-diamines is reviewed. Herein, many marketed pharmaceuticals, potential therapeutics, and natural products bearing this motif of interest are discussed. Additionally, 1,2-diamines have been shown as ligands for catalysis. Due to this interest in the 1,2-diamine functionality, some current synthetic methods to access 1,2-diamines will be shown. Chapter 2 discusses the hypothesis that a Lewis basic functionality could coordinate to a metal center and allow a hydroamination reaction to occur. Hydroamination was seen as a beneficial strategy to synthesize 1,2-diamines as olefins and amines are reacted in an atom-economical fashion. Initial reaction discovery of the rhodium-catalyzed intermolecular hydroamination of N-allylimines will be shown as well as reaction development. It was found that modest to high yields and high diastereoselectivities were obtained to synthesize 1,2-diamines with this methodology. Further, reaction development of secondary and primary N-allylamines will be discussed. These substrates offer attractive methods toward synthesizing 1,2-diamines by being easy to access. When secondary N-allylamines are employed, good yield is obtained for the desired hydroamination reaction. Excitingly, primary N-allylamines were able to be used as substrates for this transformation. This substrate class offered the shortest reaction times and proved to be effective for a wide range of amine nucleophiles.","abstract_html":"Amines are a prominent functionality found throughout organic molecules, including pharmaceuticals, agrochemicals, organic materials, and organic dyes.1 However, incorporation of amines into organic frameworks in step and atom economical fashion remains a significant challenge to synthetic chemists.2–4 In chapter 1, the importance of a class of compounds, 1,2-diamines is reviewed. Herein, many marketed pharmaceuticals, potential therapeutics, and natural products bearing this motif of interest are discussed. Additionally, 1,2-diamines have been shown as ligands for catalysis. Due to this interest in the 1,2-diamine functionality, some current synthetic methods to access 1,2-diamines will be shown. Chapter 2 discusses the hypothesis that a Lewis basic functionality could coordinate to a metal center and allow a hydroamination reaction to occur. Hydroamination was seen as a beneficial strategy to synthesize 1,2-diamines as olefins and amines are reacted in an atom-economical fashion. Initial reaction discovery of the rhodium-catalyzed intermolecular hydroamination of N-allylimines will be shown as well as reaction development. It was found that modest to high yields and high diastereoselectivities were obtained to synthesize 1,2-diamines with this methodology. Further, reaction development of secondary and primary N-allylamines will be discussed. These substrates offer attractive methods toward synthesizing 1,2-diamines by being easy to access. When secondary N-allylamines are employed, good yield is obtained for the desired hydroamination reaction. Excitingly, primary N-allylamines were able to be used as substrates for this transformation. This substrate class offered the shortest reaction times and proved to be effective for a wide range of amine nucleophiles.","abstract_has_math":false,"creators":["Ickes, Andrew R"],"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"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2017,"date_issued":"2017-03-01T17:01:51Z","date_published":"2017-03-01T17:01:51Z","updated_at":"2026-07-22T22:26:37Z","subjects":["rhodium","hydroamination","intermolecular","stereoselective","chemoselective"],"languages":["en"],"rights":["Copyright 2016 Andrew Ickes"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/95603","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Hull, Kami"]},{"key":"dc:creator","label":"Author","values":["Ickes, Andrew R"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2017-03-01T17:01:51Z","2019-03-02T10:15:18Z","2016-12-02","2016-12"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Thesis"]},{"key":"thesis:degree_name","label":"Degree Name","values":["M.S."]},{"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":["rhodium","hydroamination","intermolecular","stereoselective","chemoselective"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2016 Andrew Ickes"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/95603"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Amines are a prominent functionality found throughout organic molecules, including pharmaceuticals, agrochemicals, organic materials, and organic dyes.1 However, incorporation of amines into organic frameworks in step and atom economical fashion remains a significant challenge to synthetic chemists.2–4 In chapter 1, the importance of a class of compounds, 1,2-diamines is reviewed. Herein, many marketed pharmaceuticals, potential therapeutics, and natural products bearing this motif of interest are discussed. Additionally, 1,2-diamines have been shown as ligands for catalysis. Due to this interest in the 1,2-diamine functionality, some current synthetic methods to access 1,2-diamines will be shown. Chapter 2 discusses the hypothesis that a Lewis basic functionality could coordinate to a metal center and allow a hydroamination reaction to occur. Hydroamination was seen as a beneficial strategy to synthesize 1,2-diamines as olefins and amines are reacted in an atom-economical fashion. Initial reaction discovery of the rhodium-catalyzed intermolecular hydroamination of N-allylimines will be shown as well as reaction development. It was found that modest to high yields and high diastereoselectivities were obtained to synthesize 1,2-diamines with this methodology. Further, reaction development of secondary and primary N-allylamines will be discussed. These substrates offer attractive methods toward synthesizing 1,2-diamines by being easy to access. When secondary N-allylamines are employed, good yield is obtained for the desired hydroamination reaction. Excitingly, primary N-allylamines were able to be used as substrates for this transformation. This substrate class offered the shortest reaction times and proved to be effective for a wide range of amine nucleophiles.","Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2018-12-01","The student, Andrew Ickes, accepted the attached license on 2016-12-01 at 10:52.","The student, Andrew Ickes, submitted this Thesis for approval on 2016-12-01 at 10:58.","This Thesis was approved for publication on 2016-12-02 at 14:51.","DSpace SAF Submission Ingestion Package generated from Vireo submission #10393 on 2017-02-28 at 14:42:43","Made available in DSpace on 2017-03-01T17:01:51Z (GMT). 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Herein, many marketed pharmaceuticals, potential therapeutics, and natural products bearing this motif of interest are discussed. Additionally, 1,2-diamines have been shown as ligands for catalysis. Due to this interest in the 1,2-diamine functionality, some current synthetic methods to access 1,2-diamines will be shown. Chapter 2 discusses the hypothesis that a Lewis basic functionality could coordinate to a metal center and allow a hydroamination reaction to occur. Hydroamination was seen as a beneficial strategy to synthesize 1,2-diamines as olefins and amines are reacted in an atom-economical fashion. Initial reaction discovery of the rhodium-catalyzed intermolecular hydroamination of N-allylimines will be shown as well as reaction development. It was found that modest to high yields and high diastereoselectivities were obtained to synthesize 1,2-diamines with this methodology. Further, reaction development of secondary and primary N-allylamines will be discussed. These substrates offer attractive methods toward synthesizing 1,2-diamines by being easy to access. When secondary N-allylamines are employed, good yield is obtained for the desired hydroamination reaction. Excitingly, primary N-allylamines were able to be used as substrates for this transformation. This substrate class offered the shortest reaction times and proved to be effective for a wide range of amine nucleophiles.","Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2018-12-01","The student, Andrew Ickes, accepted the attached license on 2016-12-01 at 10:52.","The student, Andrew Ickes, submitted this Thesis for approval on 2016-12-01 at 10:58.","This Thesis was approved for publication on 2016-12-02 at 14:51.","DSpace SAF Submission Ingestion Package generated from Vireo submission #10393 on 2017-02-28 at 14:42:43","Made available in DSpace on 2017-03-01T17:01:51Z (GMT). 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