{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/95493"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/95493","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 oxysulfenylation of alkenes","abstract":"The Lewis base activation of Lewis acids has been harnessed in the development of an enantioselective oxysulfenylation reaction for unactivated alkenes. The weak Lewis acid N-(phenylthio)-phthalimide can be activated in the presence of a moderate Brønsted acid and chiral Lewis base donors. The resulting complex is a powerful sulfenylating agent capable of sulfenium transfer to simple mono-, di- and trisubstituted alkenes with high selectivity to form enantioenriched thiiranium ions. Stereospecific and site-selective capture of the thiiranium ions furnish vicinally functionalized thioethers. The nucleophile scope of the reaction encompasses alcohols, carboxylic acids and phenols. Both inter- and intramolecular sulfenylation reactions were realized. The reaction is highly robust and individual substrates usually did not require reoptimization. Mechanistic, X-ray crystallographic and kinetic investigations enabled a complete catalytic cycle to be formulated. The proposed cycle was supported by both kinetic data and the characterization of reaction intermediates. The turnover-limiting and enantiodetermining steps were identified as thiiranium ion formation. X-ray crystallography of the active sulfenylating agent did not immediately identify a basis for the high selectivity. Instead, the origin of selectivity in the reaction of trans-alkenes was determined to be distortion-based with the aid of computational models.","abstract_html":"The Lewis base activation of Lewis acids has been harnessed in the development of an enantioselective oxysulfenylation reaction for unactivated alkenes. The weak Lewis acid N-(phenylthio)-phthalimide can be activated in the presence of a moderate Brønsted acid and chiral Lewis base donors. The resulting complex is a powerful sulfenylating agent capable of sulfenium transfer to simple mono-, di- and trisubstituted alkenes with high selectivity to form enantioenriched thiiranium ions. Stereospecific and site-selective capture of the thiiranium ions furnish vicinally functionalized thioethers. The nucleophile scope of the reaction encompasses alcohols, carboxylic acids and phenols. Both inter- and intramolecular sulfenylation reactions were realized. The reaction is highly robust and individual substrates usually did not require reoptimization. Mechanistic, X-ray crystallographic and kinetic investigations enabled a complete catalytic cycle to be formulated. The proposed cycle was supported by both kinetic data and the characterization of reaction intermediates. The turnover-limiting and enantiodetermining steps were identified as thiiranium ion formation. X-ray crystallography of the active sulfenylating agent did not immediately identify a basis for the high selectivity. Instead, the origin of selectivity in the reaction of trans-alkenes was determined to be distortion-based with the aid of computational models.","abstract_has_math":false,"creators":["Kornfilt, David Jean Pierre"],"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.","Donk, Wilfred v","Rauchfuss, Thomas B."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2017,"date_issued":"2017-03-01T16:37:00Z","date_published":"2017-03-01T16:37:00Z","updated_at":"2026-07-22T22:26:37Z","subjects":["Catalysis","Lewis Bases","Enantioselecive","Organocatalysis"],"languages":["en"],"rights":["Copyright 2016 David Kornfilt"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/95493","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.","Donk, Wilfred v","Rauchfuss, Thomas B."]},{"key":"dc:creator","label":"Author","values":["Kornfilt, David Jean Pierre"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2017-03-01T16:37:00Z","2019-03-02T10:15:14Z","2016-11-30","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":["Catalysis","Lewis Bases","Enantioselecive","Organocatalysis"]}]},{"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 David Kornfilt"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/95493"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The Lewis base activation of Lewis acids has been harnessed in the development of an enantioselective oxysulfenylation reaction for unactivated alkenes. The weak Lewis acid N-(phenylthio)-phthalimide can be activated in the presence of a moderate Brønsted acid and chiral Lewis base donors. The resulting complex is a powerful sulfenylating agent capable of sulfenium transfer to simple mono-, di- and trisubstituted alkenes with high selectivity to form enantioenriched thiiranium ions. Stereospecific and site-selective capture of the thiiranium ions furnish vicinally functionalized thioethers. The nucleophile scope of the reaction encompasses alcohols, carboxylic acids and phenols. Both inter- and intramolecular sulfenylation reactions were realized. The reaction is highly robust and individual substrates usually did not require reoptimization. Mechanistic, X-ray crystallographic and kinetic investigations enabled a complete catalytic cycle to be formulated. The proposed cycle was supported by both kinetic data and the characterization of reaction intermediates. The turnover-limiting and enantiodetermining steps were identified as thiiranium ion formation. X-ray crystallography of the active sulfenylating agent did not immediately identify a basis for the high selectivity. Instead, the origin of selectivity in the reaction of trans-alkenes was determined to be distortion-based with the aid of computational models.","Submission published under a 24 month embargo labeled 'U of I Access', the embargo will last until 2018-12-01","The student, David Kornfilt, accepted the attached license on 2016-11-29 at 14:19.","The student, David Kornfilt, submitted this Dissertation for approval on 2016-11-29 at 14:23.","This Dissertation was approved for publication on 2016-11-30 at 12:50.","DSpace SAF Submission Ingestion Package generated from Vireo submission #10354 on 2017-02-28 at 14:37:01","Made available in DSpace on 2017-03-01T16:37:00Z (GMT). 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The weak Lewis acid N-(phenylthio)-phthalimide can be activated in the presence of a moderate Brønsted acid and chiral Lewis base donors. The resulting complex is a powerful sulfenylating agent capable of sulfenium transfer to simple mono-, di- and trisubstituted alkenes with high selectivity to form enantioenriched thiiranium ions. Stereospecific and site-selective capture of the thiiranium ions furnish vicinally functionalized thioethers. The nucleophile scope of the reaction encompasses alcohols, carboxylic acids and phenols. Both inter- and intramolecular sulfenylation reactions were realized. The reaction is highly robust and individual substrates usually did not require reoptimization. Mechanistic, X-ray crystallographic and kinetic investigations enabled a complete catalytic cycle to be formulated. The proposed cycle was supported by both kinetic data and the characterization of reaction intermediates. The turnover-limiting and enantiodetermining steps were identified as thiiranium ion formation. X-ray crystallography of the active sulfenylating agent did not immediately identify a basis for the high selectivity. Instead, the origin of selectivity in the reaction of trans-alkenes was determined to be distortion-based with the aid of computational models.","Submission published under a 24 month embargo labeled 'U of I Access', the embargo will last until 2018-12-01","The student, David Kornfilt, accepted the attached license on 2016-11-29 at 14:19.","The student, David Kornfilt, submitted this Dissertation for approval on 2016-11-29 at 14:23.","This Dissertation was approved for publication on 2016-11-30 at 12:50.","DSpace SAF Submission Ingestion Package generated from Vireo submission #10354 on 2017-02-28 at 14:37:01","Made available in DSpace on 2017-03-01T16:37:00Z (GMT). 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