{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/97622"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/97622","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Dearomative reduction of arenes through the use of arenophiles & studies towards the synthesis of cardiotonic steroids calotropin and calactin","abstract":"A novel method for the dearomative reduction of arenes through the use of N,N-arenophile, MTAD, was developed. Cheap feedstock arenes undergo photocycloaddition with MTAD, and the cycloadduct can be treated further to furnish novel 1,3-cyclohexadienes or 1,4-diamino-2- cyclohexenes. The utility of this method is shown in the synthesis of a natural product in two steps from naphthalene. Calotropin, a cardiotonic steroid, isolated from Apocynaceae plants is a highly cytotoxic natural product with anti-cancer activity. A total synthesis strategy which utilizes a NHC-catalyzed benzoin condensation, and Pd-catalyzed nucleophilic dearomatization of a phenol is described. Also described, is the semisynthetic strategy towards calotropin from estrone, where the aromatic A ring is dearomatized to introduce a C1 fragment at the para-position.","abstract_html":"A novel method for the dearomative reduction of arenes through the use of N,N-arenophile, MTAD, was developed. Cheap feedstock arenes undergo photocycloaddition with MTAD, and the cycloadduct can be treated further to furnish novel 1,3-cyclohexadienes or 1,4-diamino-2- cyclohexenes. The utility of this method is shown in the synthesis of a natural product in two steps from naphthalene. Calotropin, a cardiotonic steroid, isolated from Apocynaceae plants is a highly cytotoxic natural product with anti-cancer activity. A total synthesis strategy which utilizes a NHC-catalyzed benzoin condensation, and Pd-catalyzed nucleophilic dearomatization of a phenol is described. Also described, is the semisynthetic strategy towards calotropin from estrone, where the aromatic A ring is dearomatized to introduce a C1 fragment at the para-position.","abstract_has_math":false,"creators":["Nakamata Huynh, Stephanie Mio"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"M.S.","degree_level":"Thesis","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Sarlah, David"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2017,"date_issued":"2017-08-10T19:52:21Z","date_published":"2017-08-10T19:52:21Z","updated_at":"2026-07-22T22:24:34Z","subjects":["Organic chemistry","Total synthesis","Methodology","Dearomative functionalization"],"languages":["en"],"rights":["Copyright 2017 Stephanie Nakamata Huynh"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/97622","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Sarlah, David"]},{"key":"dc:creator","label":"Author","values":["Nakamata Huynh, Stephanie Mio"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2017-08-10T19:52:21Z","2019-08-11T09:15:35Z","2017-04-27","2017-05"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Thesis"]},{"key":"thesis:degree_name","label":"Degree Name","values":["M.S."]},{"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":["Organic chemistry","Total synthesis","Methodology","Dearomative functionalization"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2017 Stephanie Nakamata Huynh"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/97622"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["A novel method for the dearomative reduction of arenes through the use of N,N-arenophile, MTAD, was developed. Cheap feedstock arenes undergo photocycloaddition with MTAD, and the cycloadduct can be treated further to furnish novel 1,3-cyclohexadienes or 1,4-diamino-2- cyclohexenes. The utility of this method is shown in the synthesis of a natural product in two steps from naphthalene. Calotropin, a cardiotonic steroid, isolated from Apocynaceae plants is a highly cytotoxic natural product with anti-cancer activity. A total synthesis strategy which utilizes a NHC-catalyzed benzoin condensation, and Pd-catalyzed nucleophilic dearomatization of a phenol is described. Also described, is the semisynthetic strategy towards calotropin from estrone, where the aromatic A ring is dearomatized to introduce a C1 fragment at the para-position.","Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2019-05-01","The student, Stephanie Nakamata Huynh, accepted the attached license on 2017-04-21 at 14:53.","The student, Stephanie Nakamata Huynh, submitted this Thesis for approval on 2017-04-21 at 14:58.","This Thesis was approved for publication on 2017-04-27 at 17:23.","DSpace SAF Submission Ingestion Package generated from Vireo submission #10987 on 2017-08-10 at 14:32:29","Made available in DSpace on 2017-08-10T19:52:21Z (GMT). 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Cheap feedstock arenes undergo photocycloaddition with MTAD, and the cycloadduct can be treated further to furnish novel 1,3-cyclohexadienes or 1,4-diamino-2- cyclohexenes. The utility of this method is shown in the synthesis of a natural product in two steps from naphthalene. Calotropin, a cardiotonic steroid, isolated from Apocynaceae plants is a highly cytotoxic natural product with anti-cancer activity. A total synthesis strategy which utilizes a NHC-catalyzed benzoin condensation, and Pd-catalyzed nucleophilic dearomatization of a phenol is described. Also described, is the semisynthetic strategy towards calotropin from estrone, where the aromatic A ring is dearomatized to introduce a C1 fragment at the para-position.","Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2019-05-01","The student, Stephanie Nakamata Huynh, accepted the attached license on 2017-04-21 at 14:53.","The student, Stephanie Nakamata Huynh, submitted this Thesis for approval on 2017-04-21 at 14:58.","This Thesis was approved for publication on 2017-04-27 at 17:23.","DSpace SAF Submission Ingestion Package generated from Vireo submission #10987 on 2017-08-10 at 14:32:29","Made available in DSpace on 2017-08-10T19:52:21Z (GMT). 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