{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/70307"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/70307","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Annelation of Aromatic Compounds via 1-Aminoisobenzofurans","abstract":"The annelation of aromatic amides via 1-aminoisobenzofurans as transient reaction intermediates are reported. Three different methodologies are developed for generation of the aminoisobenzofurans in the presence of dienophiles. These involve: (1) the decomposition of an N,N-diisopropyl-o-((alpha)-diazomethyl) aromatic amide in the presence of a catalyst, (2) cesium fluoride induced (alpha)-elimination of an N,N-diisopropyl-o-((alpha),(alpha)'-bromotrimethylsilylmethyl)benzamide and (3) 2,2',6,6'-tetramethyl-piperidine induced 1,4-elimination of the cyclic imidate salt. In all cases, precursors can be synthesized by o-lithiation methodology.","abstract_html":"The annelation of aromatic amides via 1-aminoisobenzofurans as transient reaction intermediates are reported. Three different methodologies are developed for generation of the aminoisobenzofurans in the presence of dienophiles. These involve: (1) the decomposition of an N,N-diisopropyl-o-((alpha)-diazomethyl) aromatic amide in the presence of a catalyst, (2) cesium fluoride induced (alpha)-elimination of an N,N-diisopropyl-o-((alpha),(alpha)'-bromotrimethylsilylmethyl)benzamide and (3) 2,2',6,6'-tetramethyl-piperidine induced 1,4-elimination of the cyclic imidate salt. In all cases, precursors can be synthesized by o-lithiation methodology.","abstract_has_math":false,"creators":["Chen, Chin-Wen"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2014,"date_issued":"2014-12-15T23:18:31Z","date_published":"2014-12-15T23:18:31Z","updated_at":"2026-07-22T22:26:02Z","subjects":["Chemistry, Organic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8600145"],"render_values":[{"text":"(UMI)AAI8600145","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/70307","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Chen, Chin-Wen"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-15T23:18:31Z","10000-01-01","1985"]},{"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/2142/70307","(UMI)AAI8600145"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The annelation of aromatic amides via 1-aminoisobenzofurans as transient reaction intermediates are reported. Three different methodologies are developed for generation of the aminoisobenzofurans in the presence of dienophiles. These involve: (1) the decomposition of an N,N-diisopropyl-o-((alpha)-diazomethyl) aromatic amide in the presence of a catalyst, (2) cesium fluoride induced (alpha)-elimination of an N,N-diisopropyl-o-((alpha),(alpha)'-bromotrimethylsilylmethyl)benzamide and (3) 2,2',6,6'-tetramethyl-piperidine induced 1,4-elimination of the cyclic imidate salt. In all cases, precursors can be synthesized by o-lithiation methodology.","The intermediate 1-aminoisobenzofurans are suggested to undergo Diels-Alder reactions with dienophiles from the endo side to give an oxabicyclic compound. This compound is unstable under the reaction condition and undergoes ring-opening and hydrogen migration to give an N,N-dialkyl-2-carboxy-4-hydroxy-3,4-dihydro benzene ring annelated onto the original system. The reactions of the aminoisobenzofuran and dienophiles are regio- and stereoselective consistent with Frontier Molecular Orbital theory. The aromatic systems annelated by this approach included benzene, naphthalene and pyridine.","A comparison between ortho and benzylic metalation of secondary and tertiary benzamide has been made. When there is intramolecular competition between a primary or secondary benzylic hydrogen adjacent to the amide and an ortho hydrogen, the lithiation goes exclusively to the benzylic site. On the other hand, the metalation goes exclusively to the ortho site if the adjacent benzylic hydrogen is tertiary. A steric hindrance rationalization is provided.","Made available in DSpace on 2014-12-15T23:18:31Z (GMT). No. of bitstreams: 1 8600145.pdf: 4481651 bytes, checksum: 09a4707d8a28c2d66581d7f52d4e4ee9 (MD5) Previous issue date: 1985","Embargo set by: Seth Robbins for item 70473 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","U of I Only","152 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1985."]},{"key":"dc:title","label":"Title","values":["Annelation of Aromatic Compounds via 1-Aminoisobenzofurans"]}]}],"canonical_facts":{"dc:creator":["Chen, Chin-Wen"],"dc:date":["2014-12-15T23:18:31Z","10000-01-01","1985"],"dc:description":["The annelation of aromatic amides via 1-aminoisobenzofurans as transient reaction intermediates are reported. Three different methodologies are developed for generation of the aminoisobenzofurans in the presence of dienophiles. These involve: (1) the decomposition of an N,N-diisopropyl-o-((alpha)-diazomethyl) aromatic amide in the presence of a catalyst, (2) cesium fluoride induced (alpha)-elimination of an N,N-diisopropyl-o-((alpha),(alpha)'-bromotrimethylsilylmethyl)benzamide and (3) 2,2',6,6'-tetramethyl-piperidine induced 1,4-elimination of the cyclic imidate salt. In all cases, precursors can be synthesized by o-lithiation methodology.","The intermediate 1-aminoisobenzofurans are suggested to undergo Diels-Alder reactions with dienophiles from the endo side to give an oxabicyclic compound. This compound is unstable under the reaction condition and undergoes ring-opening and hydrogen migration to give an N,N-dialkyl-2-carboxy-4-hydroxy-3,4-dihydro benzene ring annelated onto the original system. The reactions of the aminoisobenzofuran and dienophiles are regio- and stereoselective consistent with Frontier Molecular Orbital theory. The aromatic systems annelated by this approach included benzene, naphthalene and pyridine.","A comparison between ortho and benzylic metalation of secondary and tertiary benzamide has been made. When there is intramolecular competition between a primary or secondary benzylic hydrogen adjacent to the amide and an ortho hydrogen, the lithiation goes exclusively to the benzylic site. On the other hand, the metalation goes exclusively to the ortho site if the adjacent benzylic hydrogen is tertiary. A steric hindrance rationalization is provided.","Made available in DSpace on 2014-12-15T23:18:31Z (GMT). No. of bitstreams: 1 8600145.pdf: 4481651 bytes, checksum: 09a4707d8a28c2d66581d7f52d4e4ee9 (MD5) Previous issue date: 1985","Embargo set by: Seth Robbins for item 70473 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","U of I Only","152 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1985."],"dc:identifier":["http://hdl.handle.net/2142/70307","(UMI)AAI8600145"],"dc:subject":["Chemistry, Organic"],"dc:title":["Annelation of Aromatic Compounds via 1-Aminoisobenzofurans"],"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":"2026-07-22T22:26:02Z"}