{"id":{"repo_id":"durham","oai_identifier":"oai:etheses.durham.ac.uk:617"},"canonical_url":"https://search.dev.ndltd.org/etd/durham/oai:etheses.durham.ac.uk:617","repository":{"repo_id":"durham","name":"Durham University","base_url":"http://etheses.dur.ac.uk/cgi/oai2"},"display":{"title":"METAL-CATALYSED CROSS-COUPLING REACTIONS OF NITROGEN HETEROCYCLES","abstract":"Described herein are copper-catalysed N-C heteroarylations of benzimidazole, 1-methylbenzimidazolone, imidazole and pyrrole. The products of these reactions then undergo palladium-catalysed C-C cross-couplings with aryl or heteroarylboronic acids under Suzuki-Miyaura conditions to provide a rapid entry to tris(hetero)aryl scaffolds comprising two or three N-heterocyclic rings. The sequential N-C and C-C couplings can be performed in a one-pot process. 1,5-Di(hetero)arylated-pyridin-2(1H)-one derivatives have been synthesised in good yields starting from (2-fluoro-5-pyridyl)boronic acid. The sequence comprises three steps: (i) palladium-catalysed Suzuki-Miyaura reaction; (ii) basic hydrolysis; (iii) copper-catalysed C-N coupling. X-ray crystal structures are reported for selected pyridin-2(1H)-one derivatives. These compounds are of interest as new scaffolds for drug discovery. A one-pot synthesis of 2-chloro-3,4-diiodopyridine from 2-chloropyridine is described via a Directed ortho Metallation (DoM)/Halogen Dance (HD) mechanism in 26-28% yields. By performing sequential iterative Suzuki-Miyaura cross-couplings using a variety of functionalised heteroaryl and arylboronic acids, a series of novel 2,3,4-triheteroarylpyridine scaffolds have been accessed in synthetically viable yields, including sterically hindered derivatives. An iterative two-fold Sonogashira/Suzuki-Miyaura reaction sequence gave access to 5-[3,4-bis(2-phenylethynyl)pyridine-2-yl]-2-fluoropyridine in 48% overall yield. Disclosed is a novel route towards benzimidazolo[1,2-f]phenanthridines starting from 4-tert-butyl-N-(2-iodophenyl)benzamide via a intermolecular palladium-catalysed N-C bond formation and dehydration to form 2-(4-tert-butylphenyl)-1-(2-bromophenyl)-1H-benzo[d]imidazole. Performing an intramolecular C-H activation reaction on this provided 6-tert-butylbenzimidazolo[1,2-f]phenanthridine. This compound could be of interest to materials science or as a new scaffold for drug discovery. Synthesis of novel soluble, shielding auxiliary ligand 4-(4-(2-ethylhexyloxy)-2,6-dimethylphenyl)pyridine-2-carboxylic acid (G1pic) has been achieved via a five step synthesis from commercially available starting materials utilising the Suzuki-Miyaura reaction on demanding substrates. A route towards a more shielded auxiliary ligand have been explored eventually providing 3-(4-pyridyl)-1,5-bis(4-(2-ethylhexyloxy)phenyl)-2,4-dimethylbenzene as an intermediate for future work. Ir(III) complexes have been synthesised with G1pic and picolinic acid.","abstract_html":"Described herein are copper-catalysed N-C heteroarylations of benzimidazole, 1-methylbenzimidazolone, imidazole and pyrrole. The products of these reactions then undergo palladium-catalysed C-C cross-couplings with aryl or heteroarylboronic acids under Suzuki-Miyaura conditions to provide a rapid entry to tris(hetero)aryl scaffolds comprising two or three N-heterocyclic rings. The sequential N-C and C-C couplings can be performed in a one-pot process. 1,5-Di(hetero)arylated-pyridin-2(1H)-one derivatives have been synthesised in good yields starting from (2-fluoro-5-pyridyl)boronic acid. The sequence comprises three steps: (i) palladium-catalysed Suzuki-Miyaura reaction; (ii) basic hydrolysis; (iii) copper-catalysed C-N coupling. X-ray crystal structures are reported for selected pyridin-2(1H)-one derivatives. These compounds are of interest as new scaffolds for drug discovery. A one-pot synthesis of 2-chloro-3,4-diiodopyridine from 2-chloropyridine is described via a Directed ortho Metallation (DoM)/Halogen Dance (HD) mechanism in 26-28% yields. By performing sequential iterative Suzuki-Miyaura cross-couplings using a variety of functionalised heteroaryl and arylboronic acids, a series of novel 2,3,4-triheteroarylpyridine scaffolds have been accessed in synthetically viable yields, including sterically hindered derivatives. An iterative two-fold Sonogashira/Suzuki-Miyaura reaction sequence gave access to 5-[3,4-bis(2-phenylethynyl)pyridine-2-yl]-2-fluoropyridine in 48% overall yield. Disclosed is a novel route towards benzimidazolo[1,2-f]phenanthridines starting from 4-tert-butyl-N-(2-iodophenyl)benzamide via a intermolecular palladium-catalysed N-C bond formation and dehydration to form 2-(4-tert-butylphenyl)-1-(2-bromophenyl)-1H-benzo[d]imidazole. Performing an intramolecular C-H activation reaction on this provided 6-tert-butylbenzimidazolo[1,2-f]phenanthridine. This compound could be of interest to materials science or as a new scaffold for drug discovery. Synthesis of novel soluble, shielding auxiliary ligand 4-(4-(2-ethylhexyloxy)-2,6-dimethylphenyl)pyridine-2-carboxylic acid (G1pic) has been achieved via a five step synthesis from commercially available starting materials utilising the Suzuki-Miyaura reaction on demanding substrates. A route towards a more shielded auxiliary ligand have been explored eventually providing 3-(4-pyridyl)-1,5-bis(4-(2-ethylhexyloxy)phenyl)-2,4-dimethylbenzene as an intermediate for future work. Ir(III) complexes have been synthesised with G1pic and picolinic acid.","abstract_has_math":false,"creators":["Siddle, James Spencer"],"institution":"Durham University","degree_name":"PhD","degree_level":"doctoral","degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2010,"date_issued":"2010","date_published":"2010","updated_at":"2026-07-24T02:11:12Z","subjects":[],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":null,"outbound_label":null,"outbound_source":null},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Siddle, James Spencer"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2010"]},{"key":"dc:date.issued","label":"Date","values":["2010"]},{"key":"dc:publisher.department","label":"Dc Publisher Department","values":["Chemistry, Department of"]},{"key":"dc:publisher.institution","label":"Dc Publisher Institution","values":["Durham University"]},{"key":"dc:relation.isreferencedby","label":"Dc Relation Isreferencedby","values":["https://etheses.durham.ac.uk/id/eprint/617/"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"dc:type.qualificationlevel","label":"Dc Type Qualificationlevel","values":["doctoral"]},{"key":"dc:type.qualificationname","label":"Dc Type Qualificationname","values":["PhD"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://etheses.durham.ac.uk/id/eprint/617/1/THESIS_JAMIE_SIDDLE.pdf"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Described herein are copper-catalysed N-C heteroarylations of benzimidazole, 1-methylbenzimidazolone, imidazole and pyrrole. The products of these reactions then undergo palladium-catalysed C-C cross-couplings with aryl or heteroarylboronic acids under Suzuki-Miyaura conditions to provide a rapid entry to tris(hetero)aryl scaffolds comprising two or three N-heterocyclic rings. The sequential N-C and C-C couplings can be performed in a one-pot process. 1,5-Di(hetero)arylated-pyridin-2(1H)-one derivatives have been synthesised in good yields starting from (2-fluoro-5-pyridyl)boronic acid. The sequence comprises three steps: (i) palladium-catalysed Suzuki-Miyaura reaction; (ii) basic hydrolysis; (iii) copper-catalysed C-N coupling. X-ray crystal structures are reported for selected pyridin-2(1H)-one derivatives. These compounds are of interest as new scaffolds for drug discovery. A one-pot synthesis of 2-chloro-3,4-diiodopyridine from 2-chloropyridine is described via a Directed ortho Metallation (DoM)/Halogen Dance (HD) mechanism in 26-28% yields. By performing sequential iterative Suzuki-Miyaura cross-couplings using a variety of functionalised heteroaryl and arylboronic acids, a series of novel 2,3,4-triheteroarylpyridine scaffolds have been accessed in synthetically viable yields, including sterically hindered derivatives. An iterative two-fold Sonogashira/Suzuki-Miyaura reaction sequence gave access to 5-[3,4-bis(2-phenylethynyl)pyridine-2-yl]-2-fluoropyridine in 48% overall yield. Disclosed is a novel route towards benzimidazolo[1,2-f]phenanthridines starting from 4-tert-butyl-N-(2-iodophenyl)benzamide via a intermolecular palladium-catalysed N-C bond formation and dehydration to form 2-(4-tert-butylphenyl)-1-(2-bromophenyl)-1H-benzo[d]imidazole. Performing an intramolecular C-H activation reaction on this provided 6-tert-butylbenzimidazolo[1,2-f]phenanthridine. This compound could be of interest to materials science or as a new scaffold for drug discovery. Synthesis of novel soluble, shielding auxiliary ligand 4-(4-(2-ethylhexyloxy)-2,6-dimethylphenyl)pyridine-2-carboxylic acid (G1pic) has been achieved via a five step synthesis from commercially available starting materials utilising the Suzuki-Miyaura reaction on demanding substrates. A route towards a more shielded auxiliary ligand have been explored eventually providing 3-(4-pyridyl)-1,5-bis(4-(2-ethylhexyloxy)phenyl)-2,4-dimethylbenzene as an intermediate for future work. Ir(III) complexes have been synthesised with G1pic and picolinic acid."]},{"key":"dc:format","label":"Dc Format","values":["text"]},{"key":"dc:title","label":"Title","values":["METAL-CATALYSED CROSS-COUPLING REACTIONS OF NITROGEN HETEROCYCLES"]}]}],"canonical_facts":{"dc:creator":["Siddle, James Spencer"],"dc:date":["2010"],"dc:date.issued":["2010"],"dc:description.abstract":["Described herein are copper-catalysed N-C heteroarylations of benzimidazole, 1-methylbenzimidazolone, imidazole and pyrrole. The products of these reactions then undergo palladium-catalysed C-C cross-couplings with aryl or heteroarylboronic acids under Suzuki-Miyaura conditions to provide a rapid entry to tris(hetero)aryl scaffolds comprising two or three N-heterocyclic rings. The sequential N-C and C-C couplings can be performed in a one-pot process. 1,5-Di(hetero)arylated-pyridin-2(1H)-one derivatives have been synthesised in good yields starting from (2-fluoro-5-pyridyl)boronic acid. The sequence comprises three steps: (i) palladium-catalysed Suzuki-Miyaura reaction; (ii) basic hydrolysis; (iii) copper-catalysed C-N coupling. X-ray crystal structures are reported for selected pyridin-2(1H)-one derivatives. These compounds are of interest as new scaffolds for drug discovery. A one-pot synthesis of 2-chloro-3,4-diiodopyridine from 2-chloropyridine is described via a Directed ortho Metallation (DoM)/Halogen Dance (HD) mechanism in 26-28% yields. By performing sequential iterative Suzuki-Miyaura cross-couplings using a variety of functionalised heteroaryl and arylboronic acids, a series of novel 2,3,4-triheteroarylpyridine scaffolds have been accessed in synthetically viable yields, including sterically hindered derivatives. An iterative two-fold Sonogashira/Suzuki-Miyaura reaction sequence gave access to 5-[3,4-bis(2-phenylethynyl)pyridine-2-yl]-2-fluoropyridine in 48% overall yield. Disclosed is a novel route towards benzimidazolo[1,2-f]phenanthridines starting from 4-tert-butyl-N-(2-iodophenyl)benzamide via a intermolecular palladium-catalysed N-C bond formation and dehydration to form 2-(4-tert-butylphenyl)-1-(2-bromophenyl)-1H-benzo[d]imidazole. Performing an intramolecular C-H activation reaction on this provided 6-tert-butylbenzimidazolo[1,2-f]phenanthridine. This compound could be of interest to materials science or as a new scaffold for drug discovery. Synthesis of novel soluble, shielding auxiliary ligand 4-(4-(2-ethylhexyloxy)-2,6-dimethylphenyl)pyridine-2-carboxylic acid (G1pic) has been achieved via a five step synthesis from commercially available starting materials utilising the Suzuki-Miyaura reaction on demanding substrates. A route towards a more shielded auxiliary ligand have been explored eventually providing 3-(4-pyridyl)-1,5-bis(4-(2-ethylhexyloxy)phenyl)-2,4-dimethylbenzene as an intermediate for future work. Ir(III) complexes have been synthesised with G1pic and picolinic acid."],"dc:format":["text"],"dc:identifier.uri":["https://etheses.durham.ac.uk/id/eprint/617/1/THESIS_JAMIE_SIDDLE.pdf"],"dc:publisher.department":["Chemistry, Department of"],"dc:publisher.institution":["Durham University"],"dc:relation.isreferencedby":["https://etheses.durham.ac.uk/id/eprint/617/"],"dc:title":["METAL-CATALYSED CROSS-COUPLING REACTIONS OF NITROGEN HETEROCYCLES"],"dc:type":["Thesis"],"dc:type.qualificationlevel":["doctoral"],"dc:type.qualificationname":["PhD"]},"updated_at":"2026-07-24T02:11:12Z"}