{"id":{"repo_id":"wvu","oai_identifier":"oai:researchrepository.wvu.edu:etd-2416"},"canonical_url":"https://search.dev.ndltd.org/etd/wvu/oai:researchrepository.wvu.edu:etd-2416","repository":{"repo_id":"wvu","name":"West Virginia University","base_url":"https://researchrepository.wvu.edu/do/oai/"},"display":{"title":"Palladium -catalyzed synthesis of carbazole derivatives and formal total syntheses of several naturally occurring carbazole alkaloids","abstract":"A mild and efficient route to substituted carbazolones has been developed. This novel procedure consists of two consecutive palladium-catalyzed reactions, an intermolecular Stille coupling followed by an intramolecular reductive N-heteroannulation. For example, 1,2-dihydro-4(3H)-carbazolone was prepared in good isolated yield (74%) by the reductive cyclization of 2-(2-nitrophenyl)-2-cyclohexen-1-one using Pd(dba)2 (6 mol%), 1,3-bis(diphenylphosphino)propane (6 mol%), 1,10-phenanthroline monohydrate (12 mol%), and carbon monoxide (90 psi) in DMF at 80°C. 2-(2-Nitrophenyl)-2-cyclohexen-1-one was prepared via a Stille coupling of 2-iodo-2-cyclohexen-1-one and 2-(tri-n-butylstannyl)-1-nitrobenzene. Many functional groups and ring sizes were tolerated in these reactions.;This novel approach to carbazolones was successfully applied to the formal total syntheses of several naturally occurring carbazole alkaloids including murrayaquinone A, murrayafoline A, koenigine-quinone A, murrayanine, dimeric O-demethylmurrayafoline A, and (+)-aspidospermidine. These new syntheses are generally more efficient and higher yielding compared to the previously reported syntheses of these natural products.;In addition, reductive cyclizations of 2-(2-nitrophenyl)-2-cycloalkenones using 10% Pd/C and 1 atm of hydrogen gas in methanol at ambient temperature yielded carbazole derivatives in excellent yields. For example, reduction of 2-(2-nitrophenyl)-2-cyclohexen-1-one gave 1,2,3,4-tetrahydrocarbazole in 95% yield. Methyl-substitution on the cyclohexenone ring regioselectively produced methyl-substituted tetrahydrocarbazoles, however substitution on the benzene ring led to mixtures of carbazole products.","abstract_html":"A mild and efficient route to substituted carbazolones has been developed. This novel procedure consists of two consecutive palladium-catalyzed reactions, an intermolecular Stille coupling followed by an intramolecular reductive N-heteroannulation. For example, 1,2-dihydro-4(3H)-carbazolone was prepared in good isolated yield (74%) by the reductive cyclization of 2-(2-nitrophenyl)-2-cyclohexen-1-one using Pd(dba)2 (6 mol%), 1,3-bis(diphenylphosphino)propane (6 mol%), 1,10-phenanthroline monohydrate (12 mol%), and carbon monoxide (90 psi) in DMF at 80°C. 2-(2-Nitrophenyl)-2-cyclohexen-1-one was prepared via a Stille coupling of 2-iodo-2-cyclohexen-1-one and 2-(tri-n-butylstannyl)-1-nitrobenzene. Many functional groups and ring sizes were tolerated in these reactions.;This novel approach to carbazolones was successfully applied to the formal total syntheses of several naturally occurring carbazole alkaloids including murrayaquinone A, murrayafoline A, koenigine-quinone A, murrayanine, dimeric O-demethylmurrayafoline A, and (+)-aspidospermidine. These new syntheses are generally more efficient and higher yielding compared to the previously reported syntheses of these natural products.;In addition, reductive cyclizations of 2-(2-nitrophenyl)-2-cycloalkenones using 10% Pd/C and 1 atm of hydrogen gas in methanol at ambient temperature yielded carbazole derivatives in excellent yields. For example, reduction of 2-(2-nitrophenyl)-2-cyclohexen-1-one gave 1,2,3,4-tetrahydrocarbazole in 95% yield. Methyl-substitution on the cyclohexenone ring regioselectively produced methyl-substituted tetrahydrocarbazoles, however substitution on the benzene ring led to mixtures of carbazole products.","abstract_has_math":false,"creators":["Scott, Tricia L."],"institution":null,"degree_name":"PhD","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Bjorn C. Soderberg."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2001,"date_issued":"2001-08-01T07:00:00Z","date_published":"2001-08-01T07:00:00Z","updated_at":"2026-07-24T06:15:40Z","subjects":["Organic chemistry"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["https://researchrepository.wvu.edu/etd/1413"],"render_values":[{"text":"https://researchrepository.wvu.edu/etd/1413","href":"https://researchrepository.wvu.edu/etd/1413","code":true}]}]},"links":{"outbound_url":"https://doi.org/10.33915/etd.1413","outbound_label":"DOI","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Bjorn C. Soderberg."]},{"key":"dc:creator","label":"Author","values":["Scott, Tricia L."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.available","label":"Dc Date Available","values":["2019-01-17T08:00:00Z"]},{"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":["PhD"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Organic chemistry"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://doi.org/10.33915/etd.1413","https://researchrepository.wvu.edu/etd/1413"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["A mild and efficient route to substituted carbazolones has been developed. This novel procedure consists of two consecutive palladium-catalyzed reactions, an intermolecular Stille coupling followed by an intramolecular reductive N-heteroannulation. For example, 1,2-dihydro-4(3H)-carbazolone was prepared in good isolated yield (74%) by the reductive cyclization of 2-(2-nitrophenyl)-2-cyclohexen-1-one using Pd(dba)2 (6 mol%), 1,3-bis(diphenylphosphino)propane (6 mol%), 1,10-phenanthroline monohydrate (12 mol%), and carbon monoxide (90 psi) in DMF at 80°C. 2-(2-Nitrophenyl)-2-cyclohexen-1-one was prepared via a Stille coupling of 2-iodo-2-cyclohexen-1-one and 2-(tri-n-butylstannyl)-1-nitrobenzene. Many functional groups and ring sizes were tolerated in these reactions.;This novel approach to carbazolones was successfully applied to the formal total syntheses of several naturally occurring carbazole alkaloids including murrayaquinone A, murrayafoline A, koenigine-quinone A, murrayanine, dimeric O-demethylmurrayafoline A, and (+)-aspidospermidine. These new syntheses are generally more efficient and higher yielding compared to the previously reported syntheses of these natural products.;In addition, reductive cyclizations of 2-(2-nitrophenyl)-2-cycloalkenones using 10% Pd/C and 1 atm of hydrogen gas in methanol at ambient temperature yielded carbazole derivatives in excellent yields. For example, reduction of 2-(2-nitrophenyl)-2-cyclohexen-1-one gave 1,2,3,4-tetrahydrocarbazole in 95% yield. Methyl-substitution on the cyclohexenone ring regioselectively produced methyl-substituted tetrahydrocarbazoles, however substitution on the benzene ring led to mixtures of carbazole products."]},{"key":"dc:title","label":"Title","values":["Palladium -catalyzed synthesis of carbazole derivatives and formal total syntheses of several naturally occurring carbazole alkaloids"]}]}],"canonical_facts":{"dc:contributor":["Bjorn C. Soderberg."],"dc:creator":["Scott, Tricia L."],"dc:date.available":["2019-01-17T08:00:00Z"],"dc:description.abstract":["A mild and efficient route to substituted carbazolones has been developed. This novel procedure consists of two consecutive palladium-catalyzed reactions, an intermolecular Stille coupling followed by an intramolecular reductive N-heteroannulation. For example, 1,2-dihydro-4(3H)-carbazolone was prepared in good isolated yield (74%) by the reductive cyclization of 2-(2-nitrophenyl)-2-cyclohexen-1-one using Pd(dba)2 (6 mol%), 1,3-bis(diphenylphosphino)propane (6 mol%), 1,10-phenanthroline monohydrate (12 mol%), and carbon monoxide (90 psi) in DMF at 80°C. 2-(2-Nitrophenyl)-2-cyclohexen-1-one was prepared via a Stille coupling of 2-iodo-2-cyclohexen-1-one and 2-(tri-n-butylstannyl)-1-nitrobenzene. Many functional groups and ring sizes were tolerated in these reactions.;This novel approach to carbazolones was successfully applied to the formal total syntheses of several naturally occurring carbazole alkaloids including murrayaquinone A, murrayafoline A, koenigine-quinone A, murrayanine, dimeric O-demethylmurrayafoline A, and (+)-aspidospermidine. These new syntheses are generally more efficient and higher yielding compared to the previously reported syntheses of these natural products.;In addition, reductive cyclizations of 2-(2-nitrophenyl)-2-cycloalkenones using 10% Pd/C and 1 atm of hydrogen gas in methanol at ambient temperature yielded carbazole derivatives in excellent yields. For example, reduction of 2-(2-nitrophenyl)-2-cyclohexen-1-one gave 1,2,3,4-tetrahydrocarbazole in 95% yield. Methyl-substitution on the cyclohexenone ring regioselectively produced methyl-substituted tetrahydrocarbazoles, however substitution on the benzene ring led to mixtures of carbazole products."],"dc:identifier":["https://doi.org/10.33915/etd.1413","https://researchrepository.wvu.edu/etd/1413"],"dc:subject":["Organic chemistry"],"dc:title":["Palladium -catalyzed synthesis of carbazole derivatives and formal total syntheses of several naturally occurring carbazole alkaloids"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["PhD"]},"updated_at":"2026-07-24T06:15:40Z"}