{"id":{"repo_id":"mit","oai_identifier":"oai:dspace.mit.edu:1721.1/147263"},"canonical_url":"https://search.dev.ndltd.org/etd/mit/oai:dspace.mit.edu:1721.1/147263","repository":{"repo_id":"mit","name":"MIT","base_url":"https://dspace.mit.edu/oai/request"},"display":{"title":"Studies on Organophosphorus Catalyzed C(SP³)–H Amination for the Synthesis of Benzimidazoles","abstract":"A PIII/PV=O-catalyzed C(sp³)–H amination has been realized for (dihydro)benzimidazole synthesis. This work reports: (1) optimization of organophosphorus-catalyzed C(sp³)–H functionalization; (2) scope studies to benzimidazoles by in situ oxidation of the corresponding dihydrobenzimidazole; and (3) insight into the reaction mechanism through in situ spectroscopic monitoring under catalytic conditions and Hammett linear free energy relationship studies. The synthetic method and mechanistic information provide insight into design principles for the expansion of C(sp³)–H functionalization reactions through PIII/PV=O O-atom transfer reactivity.","abstract_html":"A PIII/PV=O-catalyzed C(sp³)–H amination has been realized for (dihydro)benzimidazole synthesis. This work reports: (1) optimization of organophosphorus-catalyzed C(sp³)–H functionalization; (2) scope studies to benzimidazoles by in situ oxidation of the corresponding dihydrobenzimidazole; and (3) insight into the reaction mechanism through in situ spectroscopic monitoring under catalytic conditions and Hammett linear free energy relationship studies. The synthetic method and mechanistic information provide insight into design principles for the expansion of C(sp³)–H functionalization reactions through PIII/PV=O O-atom transfer reactivity.","abstract_has_math":false,"creators":["Pombar, Gisselle"],"institution":"Massachusetts Institute of Technology","degree_name":"Master","degree_level":null,"degree_discipline":null,"degree_department":"Massachusetts Institute of Technology. Department of Chemistry","school":null,"contributors":[],"advisors":["Radosevich, Alexander T."],"committee_chairs":[],"committee_members":[],"year":2022,"date_issued":"2022-09","date_published":"2022-09","updated_at":"2026-07-22T22:21:28Z","subjects":[],"languages":[],"rights":["In Copyright - Educational Use Permitted","Copyright MIT"],"rights_urls":["http://rightsstatements.org/page/InC-EDU/1.0/"],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/1721.1/147263","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Radosevich, Alexander T."]},{"key":"dc:contributor.department","label":"Department","values":["Massachusetts Institute of Technology. Department of Chemistry"]},{"key":"dc:creator","label":"Author","values":["Pombar, Gisselle"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2023-01-19T18:41:17Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2023-01-19T18:41:17Z"]},{"key":"dc:date.issued","label":"Date","values":["2022-09"]},{"key":"dc:publisher","label":"Institution","values":["Massachusetts Institute of Technology"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Master","Master of Science in Chemistry"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:rights","label":"Dc Rights","values":["In Copyright - Educational Use Permitted","Copyright MIT"]},{"key":"dc:rights.uri","label":"Rights URI","values":["http://rightsstatements.org/page/InC-EDU/1.0/"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://hdl.handle.net/1721.1/147263"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["A PIII/PV=O-catalyzed C(sp³)–H amination has been realized for (dihydro)benzimidazole synthesis. This work reports: (1) optimization of organophosphorus-catalyzed C(sp³)–H functionalization; (2) scope studies to benzimidazoles by in situ oxidation of the corresponding dihydrobenzimidazole; and (3) insight into the reaction mechanism through in situ spectroscopic monitoring under catalytic conditions and Hammett linear free energy relationship studies. The synthetic method and mechanistic information provide insight into design principles for the expansion of C(sp³)–H functionalization reactions through PIII/PV=O O-atom transfer reactivity."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["S.M."]},{"key":"dc:title","label":"Title","values":["Studies on Organophosphorus Catalyzed C(SP³)–H Amination for the Synthesis of Benzimidazoles"]}]}],"canonical_facts":{"dc:contributor.advisor":["Radosevich, Alexander T."],"dc:contributor.department":["Massachusetts Institute of Technology. Department of Chemistry"],"dc:creator":["Pombar, Gisselle"],"dc:date.accessioned":["2023-01-19T18:41:17Z"],"dc:date.available":["2023-01-19T18:41:17Z"],"dc:date.issued":["2022-09"],"dc:description.abstract":["A PIII/PV=O-catalyzed C(sp³)–H amination has been realized for (dihydro)benzimidazole synthesis. This work reports: (1) optimization of organophosphorus-catalyzed C(sp³)–H functionalization; (2) scope studies to benzimidazoles by in situ oxidation of the corresponding dihydrobenzimidazole; and (3) insight into the reaction mechanism through in situ spectroscopic monitoring under catalytic conditions and Hammett linear free energy relationship studies. The synthetic method and mechanistic information provide insight into design principles for the expansion of C(sp³)–H functionalization reactions through PIII/PV=O O-atom transfer reactivity."],"dc:description.degree":["S.M."],"dc:identifier.uri":["https://hdl.handle.net/1721.1/147263"],"dc:publisher":["Massachusetts Institute of Technology"],"dc:rights":["In Copyright - Educational Use Permitted","Copyright MIT"],"dc:rights.uri":["http://rightsstatements.org/page/InC-EDU/1.0/"],"dc:title":["Studies on Organophosphorus Catalyzed C(SP³)–H Amination for the Synthesis of Benzimidazoles"],"dc:type":["Thesis"],"thesis:degree_name":["Master","Master of Science in Chemistry"]},"updated_at":"2026-07-22T22:21:28Z"}