{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/108470"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/108470","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Stereoselective synthesis of 1,2-disubstitued βeta-amino alcohols and amino thiols","abstract":"This thesis covers the development and implementation of two distinct methodologies, both of which provide access to enantiomerically enriched, vicinally functionalized products. Chapter 1 provides background and a brief introduction of the activation of Group 16 Lewis acids by Lewis bases. Chapter 2 details a method for the catalytic, enantioselective, intermolecular, 1,2-sulfenoamination of alkenes. Functionalization is achieved through the intermediacy of an enantioenriched, configurationally stable thiiranium ion generated by Lewis base activation of a readily available sulfur electrophile. An expedited reaction optimization was achieved by employing multivariate Design of Experiment optimization ultimately resulting for a diverse set of anilines and benzylamines react with different styrenes to afford products in good yield and stereoselectivity. Downstream manipulation of the products is facilitated by deprotonation of the amines to enable carbon-sulfur bond cleavage. Chapter 3 of this thesis covers the identification of a method amenable to the rapid construction of diverse libraries of 1,2-amino alcohols. A number of methods are examined prior to the identification of 1,2-conjugate addition of aryl and alkyl lithium reagents to Ellman sulfonimines. The use of lithium reagents is key to overcome modest diastereoselectivity and poor reaction rates. A brief scope is explored and stereochemical models are discussed.","abstract_html":"This thesis covers the development and implementation of two distinct methodologies, both of which provide access to enantiomerically enriched, vicinally functionalized products. Chapter 1 provides background and a brief introduction of the activation of Group 16 Lewis acids by Lewis bases. Chapter 2 details a method for the catalytic, enantioselective, intermolecular, 1,2-sulfenoamination of alkenes. Functionalization is achieved through the intermediacy of an enantioenriched, configurationally stable thiiranium ion generated by Lewis base activation of a readily available sulfur electrophile. An expedited reaction optimization was achieved by employing multivariate Design of Experiment optimization ultimately resulting for a diverse set of anilines and benzylamines react with different styrenes to afford products in good yield and stereoselectivity. Downstream manipulation of the products is facilitated by deprotonation of the amines to enable carbon-sulfur bond cleavage. Chapter 3 of this thesis covers the identification of a method amenable to the rapid construction of diverse libraries of 1,2-amino alcohols. A number of methods are examined prior to the identification of 1,2-conjugate addition of aryl and alkyl lithium reagents to Ellman sulfonimines. The use of lithium reagents is key to overcome modest diastereoselectivity and poor reaction rates. A brief scope is explored and stereochemical models are discussed.","abstract_has_math":false,"creators":["Roth, Aaron"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Denmark, Scott E","Sarlah, David","Hergenrother, Paul","Mehta, Angad"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2020,"date_issued":"2020-10-07T20:59:44Z","date_published":"2020-10-07T20:59:44Z","updated_at":"2026-07-22T22:24:48Z","subjects":["Lewis base Catalysis, Stereoselective, Enantioselective"],"languages":["en"],"rights":["Copyright 2020 Aaron Roth"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/108470","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Denmark, Scott E","Sarlah, David","Hergenrother, Paul","Mehta, Angad"]},{"key":"dc:creator","label":"Author","values":["Roth, Aaron"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2020-10-07T20:59:44Z","2020-07-14","2020-08"]},{"key":"dc:type","label":"Dc Type","values":["text","Thesis"]},{"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":["Lewis base Catalysis, Stereoselective, Enantioselective"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2020 Aaron Roth"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/108470"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["This thesis covers the development and implementation of two distinct methodologies, both of which provide access to enantiomerically enriched, vicinally functionalized products. Chapter 1 provides background and a brief introduction of the activation of Group 16 Lewis acids by Lewis bases. Chapter 2 details a method for the catalytic, enantioselective, intermolecular, 1,2-sulfenoamination of alkenes. Functionalization is achieved through the intermediacy of an enantioenriched, configurationally stable thiiranium ion generated by Lewis base activation of a readily available sulfur electrophile. An expedited reaction optimization was achieved by employing multivariate Design of Experiment optimization ultimately resulting for a diverse set of anilines and benzylamines react with different styrenes to afford products in good yield and stereoselectivity. Downstream manipulation of the products is facilitated by deprotonation of the amines to enable carbon-sulfur bond cleavage. Chapter 3 of this thesis covers the identification of a method amenable to the rapid construction of diverse libraries of 1,2-amino alcohols. A number of methods are examined prior to the identification of 1,2-conjugate addition of aryl and alkyl lithium reagents to Ellman sulfonimines. The use of lithium reagents is key to overcome modest diastereoselectivity and poor reaction rates. A brief scope is explored and stereochemical models are discussed.","Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2020-10-02 without embargo terms","The student, Aaron Roth, accepted the attached license on 2020-07-09 at 15:30.","The student, Aaron Roth, submitted this Dissertation for approval on 2020-07-09 at 15:37.","This Dissertation was approved for publication on 2020-07-14 at 11:49.","DSpace SAF Submission Ingestion Package generated from Vireo submission #15552 on 2020-10-02 at 15:12:54","Made available in DSpace on 2020-10-07T20:59:44Z (GMT). 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Chapter 2 details a method for the catalytic, enantioselective, intermolecular, 1,2-sulfenoamination of alkenes. Functionalization is achieved through the intermediacy of an enantioenriched, configurationally stable thiiranium ion generated by Lewis base activation of a readily available sulfur electrophile. An expedited reaction optimization was achieved by employing multivariate Design of Experiment optimization ultimately resulting for a diverse set of anilines and benzylamines react with different styrenes to afford products in good yield and stereoselectivity. Downstream manipulation of the products is facilitated by deprotonation of the amines to enable carbon-sulfur bond cleavage. Chapter 3 of this thesis covers the identification of a method amenable to the rapid construction of diverse libraries of 1,2-amino alcohols. A number of methods are examined prior to the identification of 1,2-conjugate addition of aryl and alkyl lithium reagents to Ellman sulfonimines. 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