{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/95503"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/95503","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Lewis base catalyzed enantioselective sulfenoamination of alkenes","abstract":"The concept of Lewis base activation of Lewis acid has been successfully applied to the enantioselective sulfenoamination of olefins. The unreactive, achiral Lewis acidic sulfenylating agent, N-arylthiophthalimide, is activated by the coordination of a chiral Lewis base, binaphthyl-derived selenophosphoramide, in presence of a Brønsted acid as a co-catalyst. The Lewis base-acid adduct exhibits a strong sulfenylating ability towards various olefins with formation of enantioenriched thiiranium ion intermediates. These configurationally stable thiiranium ions are stereospecifically captured by amines and anilines to afford nitrogen-containing heterocycles, such as piperidines, azepanes, and tetrahydroquinolines. In the course of developing an enantioselective carbosulfenylation of alkenes, a seemingly contradicting phenomenon of a catalyst inhibiting a stoichiometric reaction was observed. In the absence of catalyst, the background reaction rates were comparable to or greater than the catalyzed process, despite the observation of highly enantioenriched product when a chiral, nonracemic catalyst was employed. Detailed kinetic and spectroscopic studies revealed that the conversion of the Lewis base pre-catalyst to the catalytically active species was responsible for the observed comparable reactivity. Specifically, the equimolar formation of the byproducts of the catalyst activation, sulfonate ion and phthalimide, buffered the Brønsted acid, resulting in inhibition of the uncatalyzed racemic pathway. Therefore, the operating background reaction under catalytic conditions cannot be represented by simply omitting the catalyst.","abstract_html":"The concept of Lewis base activation of Lewis acid has been successfully applied to the enantioselective sulfenoamination of olefins. The unreactive, achiral Lewis acidic sulfenylating agent, N-arylthiophthalimide, is activated by the coordination of a chiral Lewis base, binaphthyl-derived selenophosphoramide, in presence of a Brønsted acid as a co-catalyst. The Lewis base-acid adduct exhibits a strong sulfenylating ability towards various olefins with formation of enantioenriched thiiranium ion intermediates. These configurationally stable thiiranium ions are stereospecifically captured by amines and anilines to afford nitrogen-containing heterocycles, such as piperidines, azepanes, and tetrahydroquinolines. In the course of developing an enantioselective carbosulfenylation of alkenes, a seemingly contradicting phenomenon of a catalyst inhibiting a stoichiometric reaction was observed. In the absence of catalyst, the background reaction rates were comparable to or greater than the catalyzed process, despite the observation of highly enantioenriched product when a chiral, nonracemic catalyst was employed. Detailed kinetic and spectroscopic studies revealed that the conversion of the Lewis base pre-catalyst to the catalytically active species was responsible for the observed comparable reactivity. Specifically, the equimolar formation of the byproducts of the catalyst activation, sulfonate ion and phthalimide, buffered the Brønsted acid, resulting in inhibition of the uncatalyzed racemic pathway. Therefore, the operating background reaction under catalytic conditions cannot be represented by simply omitting the catalyst.","abstract_has_math":false,"creators":["Chi, Hyungmin"],"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.","Burke, Martin D.","van der Donk, Wilfred A.","Rauchfuss, Thomas B."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2017,"date_issued":"2017-03-01T16:37:04Z","date_published":"2017-03-01T16:37:04Z","updated_at":"2026-07-22T22:26:37Z","subjects":["Sulfenoamination","Enantioselective catalysis","Lewis base","Negative catalysis"],"languages":["en"],"rights":["Copyright 2016 Hyungmin Chi"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/95503","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Denmark, Scott E.","Burke, Martin D.","van der Donk, Wilfred A.","Rauchfuss, Thomas B."]},{"key":"dc:creator","label":"Author","values":["Chi, Hyungmin"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2017-03-01T16:37:04Z","2019-03-02T10:15:27Z","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":["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":["Sulfenoamination","Enantioselective catalysis","Lewis base","Negative catalysis"]}]},{"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 Hyungmin Chi"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/95503"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The concept of Lewis base activation of Lewis acid has been successfully applied to the enantioselective sulfenoamination of olefins. The unreactive, achiral Lewis acidic sulfenylating agent, N-arylthiophthalimide, is activated by the coordination of a chiral Lewis base, binaphthyl-derived selenophosphoramide, in presence of a Brønsted acid as a co-catalyst. The Lewis base-acid adduct exhibits a strong sulfenylating ability towards various olefins with formation of enantioenriched thiiranium ion intermediates. These configurationally stable thiiranium ions are stereospecifically captured by amines and anilines to afford nitrogen-containing heterocycles, such as piperidines, azepanes, and tetrahydroquinolines. In the course of developing an enantioselective carbosulfenylation of alkenes, a seemingly contradicting phenomenon of a catalyst inhibiting a stoichiometric reaction was observed. In the absence of catalyst, the background reaction rates were comparable to or greater than the catalyzed process, despite the observation of highly enantioenriched product when a chiral, nonracemic catalyst was employed. Detailed kinetic and spectroscopic studies revealed that the conversion of the Lewis base pre-catalyst to the catalytically active species was responsible for the observed comparable reactivity. Specifically, the equimolar formation of the byproducts of the catalyst activation, sulfonate ion and phthalimide, buffered the Brønsted acid, resulting in inhibition of the uncatalyzed racemic pathway. Therefore, the operating background reaction under catalytic conditions cannot be represented by simply omitting the catalyst.","Submission published under a 24 month embargo labeled 'U of I Access', the embargo will last until 2018-12-01","The student, Hyungmin Chi, accepted the attached license on 2016-12-01 at 12:03.","The student, Hyungmin Chi, submitted this Dissertation for approval on 2016-12-01 at 12:14.","This Dissertation was approved for publication on 2016-12-02 at 11:30.","DSpace SAF Submission Ingestion Package generated from Vireo submission #10395 on 2017-02-28 at 14:37:10","Made available in DSpace on 2017-03-01T16:37:04Z (GMT). No. of bitstreams: 2 CHI-DISSERTATION-2016.pdf: 12717846 bytes, checksum: 77819cce50e91d7cd406880d43b87237 (MD5) LICENSE.txt: 4209 bytes, checksum: 1e4a968934263735f24581b36a522338 (MD5) Previous issue date: 2016-12-02","Embargo set by: Seth Robbins for item 98619 Lift date: 2019-03-01T16:37:19Z Reason: Author requested U of Illinois access only (OA after 2yrs) in Vireo ETD system","U of I Only Restriction Lifted for Item 98619 on 2019-03-02T10:15:27Z."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Lewis base catalyzed enantioselective sulfenoamination of alkenes"]}]}],"canonical_facts":{"dc:contributor":["Denmark, Scott E.","Burke, Martin D.","van der Donk, Wilfred A.","Rauchfuss, Thomas B."],"dc:creator":["Chi, Hyungmin"],"dc:date":["2017-03-01T16:37:04Z","2019-03-02T10:15:27Z","2016-12-02","2016-12"],"dc:description":["The concept of Lewis base activation of Lewis acid has been successfully applied to the enantioselective sulfenoamination of olefins. The unreactive, achiral Lewis acidic sulfenylating agent, N-arylthiophthalimide, is activated by the coordination of a chiral Lewis base, binaphthyl-derived selenophosphoramide, in presence of a Brønsted acid as a co-catalyst. The Lewis base-acid adduct exhibits a strong sulfenylating ability towards various olefins with formation of enantioenriched thiiranium ion intermediates. These configurationally stable thiiranium ions are stereospecifically captured by amines and anilines to afford nitrogen-containing heterocycles, such as piperidines, azepanes, and tetrahydroquinolines. In the course of developing an enantioselective carbosulfenylation of alkenes, a seemingly contradicting phenomenon of a catalyst inhibiting a stoichiometric reaction was observed. In the absence of catalyst, the background reaction rates were comparable to or greater than the catalyzed process, despite the observation of highly enantioenriched product when a chiral, nonracemic catalyst was employed. Detailed kinetic and spectroscopic studies revealed that the conversion of the Lewis base pre-catalyst to the catalytically active species was responsible for the observed comparable reactivity. Specifically, the equimolar formation of the byproducts of the catalyst activation, sulfonate ion and phthalimide, buffered the Brønsted acid, resulting in inhibition of the uncatalyzed racemic pathway. Therefore, the operating background reaction under catalytic conditions cannot be represented by simply omitting the catalyst.","Submission published under a 24 month embargo labeled 'U of I Access', the embargo will last until 2018-12-01","The student, Hyungmin Chi, accepted the attached license on 2016-12-01 at 12:03.","The student, Hyungmin Chi, submitted this Dissertation for approval on 2016-12-01 at 12:14.","This Dissertation was approved for publication on 2016-12-02 at 11:30.","DSpace SAF Submission Ingestion Package generated from Vireo submission #10395 on 2017-02-28 at 14:37:10","Made available in DSpace on 2017-03-01T16:37:04Z (GMT). No. of bitstreams: 2 CHI-DISSERTATION-2016.pdf: 12717846 bytes, checksum: 77819cce50e91d7cd406880d43b87237 (MD5) LICENSE.txt: 4209 bytes, checksum: 1e4a968934263735f24581b36a522338 (MD5) Previous issue date: 2016-12-02","Embargo set by: Seth Robbins for item 98619 Lift date: 2019-03-01T16:37:19Z Reason: Author requested U of Illinois access only (OA after 2yrs) in Vireo ETD system","U of I Only Restriction Lifted for Item 98619 on 2019-03-02T10:15:27Z."],"dc:format":["application/pdf"],"dc:identifier":["http://hdl.handle.net/2142/95503"],"dc:language":["en"],"dc:rights":["Copyright 2016 Hyungmin Chi"],"dc:subject":["Sulfenoamination","Enantioselective catalysis","Lewis base","Negative catalysis"],"dc:title":["Lewis base catalyzed enantioselective sulfenoamination of alkenes"],"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":"2026-07-22T22:26:37Z"}