{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/72269"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/72269","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Intramolecular Triplex Diels-Alder Reaction With Cyclic Dienes Electron Transfer Induced Nitrogen-Oxygen Bond Cleavage Reactions of N-Aryloxypyridinium and N,n'-Dialkoxybipyridinium Salts","abstract":"U of I Only","abstract_html":"U of I Only","abstract_has_math":false,"creators":["Wolfle, Ingrid"],"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":"2014-12-17T21:29:01Z","date_published":"2014-12-17T21:29:01Z","updated_at":"2026-07-22T22:26:06Z","subjects":["Chemistry, Organic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI9236627"],"render_values":[{"text":"(UMI)AAI9236627","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/72269","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":["Wolfle, Ingrid"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-17T21:29:01Z","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/2142/72269","(UMI)AAI9236627"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["U of I Only","113 p.","Part 1. The intramolecular triplex Diels-Alder reaction of 1-alkenylsubstituted 2,4-cyclohexadienes was investigated with several sensitizers. The (4+2) cycloaddition proceeds in good yield when the dienophile carries a phenyl substituent, but not at all when it is methylsubstituted. For the substrates which have a phenylsubstituted dienophile, cycloaddition proceeds endo-selective and with retention of dienophile stereochemistry. The efficiency of cyclization depends on the length of the tether connecting diene and dienophile. The (4+2) adduct is formed in 88% yield when the tether contains three carbons. When the chain is one carbon longer, dyotropic hydrogen transfer competes with the Diels-Alder cyclization.","Part 2. Photoinduced electron transfer to N-(4-cyanophenoxy)pyridinium or N,N$\\sp\\prime$-diethoxybipyridinium salts results in cleavage of the nitrogen-oxygen bond. The efficiency of this fragmentation process depends crucially on the nature of the departing radical. When a stabilized radical such as 4-cyanophenoxy radical is produced, the rate of bond cleavage exceeds 2 $\\times$ 10$\\sp $ s$\\sp{-1}$. With an unstabilized leaving radical, this rate slows down to ca. 1 $\\times$ 10$\\sp4$ s$\\sp{-1}$.","Made available in DSpace on 2014-12-17T21:29:01Z (GMT). No. of bitstreams: 1 9236627.pdf: 4065255 bytes, checksum: b889a442e2c73ad0d42e055628eeb365 (MD5) Previous issue date: 1992","Embargo set by: Seth Robbins for item 72437 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1992."]},{"key":"dc:title","label":"Title","values":["Intramolecular Triplex Diels-Alder Reaction With Cyclic Dienes Electron Transfer Induced Nitrogen-Oxygen Bond Cleavage Reactions of N-Aryloxypyridinium and N,n'-Dialkoxybipyridinium Salts"]}]}],"canonical_facts":{"dc:contributor":["Schuster, Gary B."],"dc:creator":["Wolfle, Ingrid"],"dc:date":["2014-12-17T21:29:01Z","10000-01-01","1992"],"dc:description":["U of I Only","113 p.","Part 1. The intramolecular triplex Diels-Alder reaction of 1-alkenylsubstituted 2,4-cyclohexadienes was investigated with several sensitizers. The (4+2) cycloaddition proceeds in good yield when the dienophile carries a phenyl substituent, but not at all when it is methylsubstituted. For the substrates which have a phenylsubstituted dienophile, cycloaddition proceeds endo-selective and with retention of dienophile stereochemistry. The efficiency of cyclization depends on the length of the tether connecting diene and dienophile. The (4+2) adduct is formed in 88% yield when the tether contains three carbons. When the chain is one carbon longer, dyotropic hydrogen transfer competes with the Diels-Alder cyclization.","Part 2. Photoinduced electron transfer to N-(4-cyanophenoxy)pyridinium or N,N$\\sp\\prime$-diethoxybipyridinium salts results in cleavage of the nitrogen-oxygen bond. The efficiency of this fragmentation process depends crucially on the nature of the departing radical. When a stabilized radical such as 4-cyanophenoxy radical is produced, the rate of bond cleavage exceeds 2 $\\times$ 10$\\sp $ s$\\sp{-1}$. With an unstabilized leaving radical, this rate slows down to ca. 1 $\\times$ 10$\\sp4$ s$\\sp{-1}$.","Made available in DSpace on 2014-12-17T21:29:01Z (GMT). No. of bitstreams: 1 9236627.pdf: 4065255 bytes, checksum: b889a442e2c73ad0d42e055628eeb365 (MD5) Previous issue date: 1992","Embargo set by: Seth Robbins for item 72437 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1992."],"dc:identifier":["http://hdl.handle.net/2142/72269","(UMI)AAI9236627"],"dc:subject":["Chemistry, Organic"],"dc:title":["Intramolecular Triplex Diels-Alder Reaction With Cyclic Dienes Electron Transfer Induced Nitrogen-Oxygen Bond Cleavage Reactions of N-Aryloxypyridinium and N,n'-Dialkoxybipyridinium Salts"],"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":"2026-07-22T22:26:06Z"}