{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/72268"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/72268","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"The Triplex Diels-Alder Reaction: An Investigation of Enantioselectivity and Scope","abstract":"Part I. Enantioselective triplex Diels-Alder reaction. An investigation of the enantioselective triplex Diels-Alder reaction has been performed with optically active biaryl sensitizers, (-)1,1$\\sp\\prime$bis(2,4-dicyanonaphthalene) and (-)1,1$\\sp\\prime$bis(2,10-dicyanoanthracene). Irradiation of an optically active sensitizer in non-polar solvents containing substituted trans-$\\beta$-methylstyrenes and cyclic dienes yielded endo (4+2) adducts with enantioselectivity up to 23%. Our report is the first observation of an enantioselective photochemical cycloaddition reaction which is catalyzed by a chiral sensitizer. The mechanistic investigation suggests the presence of diastereomeric exciplexes. The advantages and limitations of the reaction are discussed along with the results from the mechanistic study. (DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI)","abstract_html":"Part I. Enantioselective triplex Diels-Alder reaction. An investigation of the enantioselective triplex Diels-Alder reaction has been performed with optically active biaryl sensitizers, (-)1,1$\\sp\\prime$bis(2,4-dicyanonaphthalene) and (-)1,1$\\sp\\prime$bis(2,10-dicyanoanthracene). Irradiation of an optically active sensitizer in non-polar solvents containing substituted trans-<span class=\"etd-inline-math\">&beta;</span>-methylstyrenes and cyclic dienes yielded endo (4+2) adducts with enantioselectivity up to 23%. Our report is the first observation of an enantioselective photochemical cycloaddition reaction which is catalyzed by a chiral sensitizer. The mechanistic investigation suggests the presence of diastereomeric exciplexes. The advantages and limitations of the reaction are discussed along with the results from the mechanistic study. (DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI)","abstract_has_math":true,"creators":["Kim, Ji-In"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Schuster, Gary B."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2014,"date_issued":"2014-12-17T21:29:00Z","date_published":"2014-12-17T21:29:00Z","updated_at":"2026-07-22T22:26:06Z","subjects":["Chemistry, Organic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI9236501"],"render_values":[{"text":"(UMI)AAI9236501","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/72268","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Schuster, Gary B."]},{"key":"dc:creator","label":"Author","values":["Kim, Ji-In"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-17T21:29:00Z","10000-01-01","1992"]},{"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":["Chemistry, Organic"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/72268","(UMI)AAI9236501"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Part I. Enantioselective triplex Diels-Alder reaction. An investigation of the enantioselective triplex Diels-Alder reaction has been performed with optically active biaryl sensitizers, (-)1,1$\\sp\\prime$bis(2,4-dicyanonaphthalene) and (-)1,1$\\sp\\prime$bis(2,10-dicyanoanthracene). Irradiation of an optically active sensitizer in non-polar solvents containing substituted trans-$\\beta$-methylstyrenes and cyclic dienes yielded endo (4+2) adducts with enantioselectivity up to 23%. Our report is the first observation of an enantioselective photochemical cycloaddition reaction which is catalyzed by a chiral sensitizer. The mechanistic investigation suggests the presence of diastereomeric exciplexes. The advantages and limitations of the reaction are discussed along with the results from the mechanistic study. (DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI)","Part II. Triplex Diels-Alder reaction with acetylenic dienophiles. An investigation of triplex Diels-Alder reaction has been carried out with sensitizers, 1,4-dicyanonaphthalene or 2,6,9,10-tetracyanoanthracene. Irradiation of a sensitizer in non-polar solvents containing acetylenic dienophiles and dienes yielded cycloaddition products. Results showed that either (4+2) or (2+2) cycloadducts are formed depending on whether the diene is cyclic or acyclic. Through product and photophysical studies, the scope and limitations of triplex Diels-Alder reaction with acetylenic dienophiles were examined.","Made available in DSpace on 2014-12-17T21:29:00Z (GMT). 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An investigation of the enantioselective triplex Diels-Alder reaction has been performed with optically active biaryl sensitizers, (-)1,1$\\sp\\prime$bis(2,4-dicyanonaphthalene) and (-)1,1$\\sp\\prime$bis(2,10-dicyanoanthracene). Irradiation of an optically active sensitizer in non-polar solvents containing substituted trans-$\\beta$-methylstyrenes and cyclic dienes yielded endo (4+2) adducts with enantioselectivity up to 23%. Our report is the first observation of an enantioselective photochemical cycloaddition reaction which is catalyzed by a chiral sensitizer. The mechanistic investigation suggests the presence of diastereomeric exciplexes. The advantages and limitations of the reaction are discussed along with the results from the mechanistic study. (DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI)","Part II. Triplex Diels-Alder reaction with acetylenic dienophiles. An investigation of triplex Diels-Alder reaction has been carried out with sensitizers, 1,4-dicyanonaphthalene or 2,6,9,10-tetracyanoanthracene. Irradiation of a sensitizer in non-polar solvents containing acetylenic dienophiles and dienes yielded cycloaddition products. Results showed that either (4+2) or (2+2) cycloadducts are formed depending on whether the diene is cyclic or acyclic. Through product and photophysical studies, the scope and limitations of triplex Diels-Alder reaction with acetylenic dienophiles were examined.","Made available in DSpace on 2014-12-17T21:29:00Z (GMT). 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