{"id":{"repo_id":"strathclyde","oai_identifier":"oai:strathclyde:7s75dc423"},"canonical_url":"https://search.dev.ndltd.org/etd/strathclyde/oai:strathclyde:7s75dc423","repository":{"repo_id":"strathclyde","name":"University of Strathclyde","base_url":"https://stax.strath.ac.uk/catalog/oai"},"display":{"title":"A novel route to fluoroarenes from trifluoroethanol","abstract":"This Thesis describes the preparation of fluoroarenes using a palladium-catalysed coupling/electrocyclisation methodology. Difluoroenolzinc coupling partners, 1-(N,N-diethylcarbamoyloxy)-2,2-difluoro-1-zinc chloride and 2,2-difluoro-1-(2'-methoxy-ethoxymethoxy)-1-zinc chloride were prepared from trifluoroethanol at near ambient temperature and underwent Negishi coupling with a range of aryl-halides. A co-solvent (N,N-dimethylpropylene urea) was necessary to generate 2,2-difluoro-1-(2'-methoxy-ethoxymethoxy)-1-zinc chloride in good yield. The zinc coupling partners were also converted to (iodo)difluoroenols which participated in Suzuki-Miyaura coupling with a range of aryl-boronic acids and potassium aryl-trifluoroborates. Side reactions of the Suzuki-Miyaura couplings were circumvented by using tertiary butanol as the reaction solvent. Low temperature preparation of trifluoroborate coupling partners, potassium 2,2-difluoro-1-(N,N-diethylcarbamoyloxy)ethenyl trifluoroborate and potassium 2,2-difluoro-1-(2'-methoxy-ethoxymethoxy)ethenyl trifluoroborate, from trifluoroethanol was also accomplished. The trifluoroborates underwent Suzuki-Miyaura coupling with a range of aryl-halides. This Suzuki-Miyaura coupling protocol was used to prepare a range of fluorinated electrocyclisation precursors in modest to good yield. Subsequent electrocyclisation afforded fluorobenzene, fluoronaphthalene and fluorophenanthrene species. The electrocyclisations were investigated computationally in an attempt to rationalise the ease/difficulty of cyclisation.","abstract_html":"This Thesis describes the preparation of fluoroarenes using a palladium-catalysed coupling/electrocyclisation methodology. Difluoroenolzinc coupling partners, 1-(N,N-diethylcarbamoyloxy)-2,2-difluoro-1-zinc chloride and 2,2-difluoro-1-(2'-methoxy-ethoxymethoxy)-1-zinc chloride were prepared from trifluoroethanol at near ambient temperature and underwent Negishi coupling with a range of aryl-halides. A co-solvent (N,N-dimethylpropylene urea) was necessary to generate 2,2-difluoro-1-(2'-methoxy-ethoxymethoxy)-1-zinc chloride in good yield. The zinc coupling partners were also converted to (iodo)difluoroenols which participated in Suzuki-Miyaura coupling with a range of aryl-boronic acids and potassium aryl-trifluoroborates. Side reactions of the Suzuki-Miyaura couplings were circumvented by using tertiary butanol as the reaction solvent. Low temperature preparation of trifluoroborate coupling partners, potassium 2,2-difluoro-1-(N,N-diethylcarbamoyloxy)ethenyl trifluoroborate and potassium 2,2-difluoro-1-(2'-methoxy-ethoxymethoxy)ethenyl trifluoroborate, from trifluoroethanol was also accomplished. The trifluoroborates underwent Suzuki-Miyaura coupling with a range of aryl-halides. This Suzuki-Miyaura coupling protocol was used to prepare a range of fluorinated electrocyclisation precursors in modest to good yield. Subsequent electrocyclisation afforded fluorobenzene, fluoronaphthalene and fluorophenanthrene species. The electrocyclisations were investigated computationally in an attempt to rationalise the ease/difficulty of cyclisation.","abstract_has_math":false,"creators":["Wilson, Peter"],"institution":"University of Strathclyde","degree_name":"phd","degree_level":"doctoral-pg","degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2014,"date_issued":"2014","date_published":"2014","updated_at":"2026-07-24T04:45:53Z","subjects":[],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier.doi","label":"DOI","values":["10.48730/0xk1-ck07"],"render_values":[{"text":"10.48730/0xk1-ck07","href":"https://doi.org/10.48730/0xk1-ck07","code":true}]},{"key":"dc:identifier","label":"Identifier","values":["T13938"],"render_values":[{"text":"T13938","href":null,"code":true}]}]},"links":{"outbound_url":"https://stax.strath.ac.uk/concern/theses/7s75dc423","outbound_label":"Repository record","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Wilson, Peter"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014"]},{"key":"dc:date.issued","label":"Date","values":["2014"]},{"key":"dc:publisher.department","label":"Dc Publisher Department","values":["Department of Pure and Applied Chemistry"]},{"key":"dc:publisher.institution","label":"Dc Publisher Institution","values":["University of Strathclyde"]},{"key":"dc:type.qualificationlevel","label":"Dc Type Qualificationlevel","values":["doctoral-pg"]},{"key":"dc:type.qualificationname","label":"Dc Type Qualificationname","values":["phd"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["T13938"]},{"key":"dc:identifier.doi","label":"DOI","values":["10.48730/0xk1-ck07"]},{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://stax.strath.ac.uk/concern/theses/7s75dc423"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["This Thesis describes the preparation of fluoroarenes using a palladium-catalysed coupling/electrocyclisation methodology. Difluoroenolzinc coupling partners, 1-(N,N-diethylcarbamoyloxy)-2,2-difluoro-1-zinc chloride and 2,2-difluoro-1-(2'-methoxy-ethoxymethoxy)-1-zinc chloride were prepared from trifluoroethanol at near ambient temperature and underwent Negishi coupling with a range of aryl-halides. A co-solvent (N,N-dimethylpropylene urea) was necessary to generate 2,2-difluoro-1-(2'-methoxy-ethoxymethoxy)-1-zinc chloride in good yield. The zinc coupling partners were also converted to (iodo)difluoroenols which participated in Suzuki-Miyaura coupling with a range of aryl-boronic acids and potassium aryl-trifluoroborates. Side reactions of the Suzuki-Miyaura couplings were circumvented by using tertiary butanol as the reaction solvent. Low temperature preparation of trifluoroborate coupling partners, potassium 2,2-difluoro-1-(N,N-diethylcarbamoyloxy)ethenyl trifluoroborate and potassium 2,2-difluoro-1-(2'-methoxy-ethoxymethoxy)ethenyl trifluoroborate, from trifluoroethanol was also accomplished. The trifluoroborates underwent Suzuki-Miyaura coupling with a range of aryl-halides. This Suzuki-Miyaura coupling protocol was used to prepare a range of fluorinated electrocyclisation precursors in modest to good yield. Subsequent electrocyclisation afforded fluorobenzene, fluoronaphthalene and fluorophenanthrene species. The electrocyclisations were investigated computationally in an attempt to rationalise the ease/difficulty of cyclisation."]},{"key":"dc:description.abstract","label":"Abstract","values":["This Thesis describes the preparation of fluoroarenes using a palladium-catalysed coupling/electrocyclisation methodology. Difluoroenolzinc coupling partners, 1-(N,N-diethylcarbamoyloxy)-2,2-difluoro-1-zinc chloride and 2,2-difluoro-1-(2'-methoxy-ethoxymethoxy)-1-zinc chloride were prepared from trifluoroethanol at near ambient temperature and underwent Negishi coupling with a range of aryl-halides. A co-solvent (N,N-dimethylpropylene urea) was necessary to generate 2,2-difluoro-1-(2'-methoxy-ethoxymethoxy)-1-zinc chloride in good yield. The zinc coupling partners were also converted to (iodo)difluoroenols which participated in Suzuki-Miyaura coupling with a range of aryl-boronic acids and potassium aryl-trifluoroborates. Side reactions of the Suzuki-Miyaura couplings were circumvented by using tertiary butanol as the reaction solvent. Low temperature preparation of trifluoroborate coupling partners, potassium 2,2-difluoro-1-(N,N-diethylcarbamoyloxy)ethenyl trifluoroborate and potassium 2,2-difluoro-1-(2'-methoxy-ethoxymethoxy)ethenyl trifluoroborate, from trifluoroethanol was also accomplished. The trifluoroborates underwent Suzuki-Miyaura coupling with a range of aryl-halides. This Suzuki-Miyaura coupling protocol was used to prepare a range of fluorinated electrocyclisation precursors in modest to good yield. Subsequent electrocyclisation afforded fluorobenzene, fluoronaphthalene and fluorophenanthrene species. The electrocyclisations were investigated computationally in an attempt to rationalise the ease/difficulty of cyclisation."]},{"key":"dc:title","label":"Title","values":["A novel route to fluoroarenes from trifluoroethanol"]}]}],"canonical_facts":{"dc:creator":["Wilson, Peter"],"dc:date":["2014"],"dc:date.issued":["2014"],"dc:description":["This Thesis describes the preparation of fluoroarenes using a palladium-catalysed coupling/electrocyclisation methodology. Difluoroenolzinc coupling partners, 1-(N,N-diethylcarbamoyloxy)-2,2-difluoro-1-zinc chloride and 2,2-difluoro-1-(2'-methoxy-ethoxymethoxy)-1-zinc chloride were prepared from trifluoroethanol at near ambient temperature and underwent Negishi coupling with a range of aryl-halides. A co-solvent (N,N-dimethylpropylene urea) was necessary to generate 2,2-difluoro-1-(2'-methoxy-ethoxymethoxy)-1-zinc chloride in good yield. The zinc coupling partners were also converted to (iodo)difluoroenols which participated in Suzuki-Miyaura coupling with a range of aryl-boronic acids and potassium aryl-trifluoroborates. Side reactions of the Suzuki-Miyaura couplings were circumvented by using tertiary butanol as the reaction solvent. Low temperature preparation of trifluoroborate coupling partners, potassium 2,2-difluoro-1-(N,N-diethylcarbamoyloxy)ethenyl trifluoroborate and potassium 2,2-difluoro-1-(2'-methoxy-ethoxymethoxy)ethenyl trifluoroborate, from trifluoroethanol was also accomplished. The trifluoroborates underwent Suzuki-Miyaura coupling with a range of aryl-halides. This Suzuki-Miyaura coupling protocol was used to prepare a range of fluorinated electrocyclisation precursors in modest to good yield. Subsequent electrocyclisation afforded fluorobenzene, fluoronaphthalene and fluorophenanthrene species. The electrocyclisations were investigated computationally in an attempt to rationalise the ease/difficulty of cyclisation."],"dc:description.abstract":["This Thesis describes the preparation of fluoroarenes using a palladium-catalysed coupling/electrocyclisation methodology. Difluoroenolzinc coupling partners, 1-(N,N-diethylcarbamoyloxy)-2,2-difluoro-1-zinc chloride and 2,2-difluoro-1-(2'-methoxy-ethoxymethoxy)-1-zinc chloride were prepared from trifluoroethanol at near ambient temperature and underwent Negishi coupling with a range of aryl-halides. A co-solvent (N,N-dimethylpropylene urea) was necessary to generate 2,2-difluoro-1-(2'-methoxy-ethoxymethoxy)-1-zinc chloride in good yield. The zinc coupling partners were also converted to (iodo)difluoroenols which participated in Suzuki-Miyaura coupling with a range of aryl-boronic acids and potassium aryl-trifluoroborates. Side reactions of the Suzuki-Miyaura couplings were circumvented by using tertiary butanol as the reaction solvent. Low temperature preparation of trifluoroborate coupling partners, potassium 2,2-difluoro-1-(N,N-diethylcarbamoyloxy)ethenyl trifluoroborate and potassium 2,2-difluoro-1-(2'-methoxy-ethoxymethoxy)ethenyl trifluoroborate, from trifluoroethanol was also accomplished. The trifluoroborates underwent Suzuki-Miyaura coupling with a range of aryl-halides. This Suzuki-Miyaura coupling protocol was used to prepare a range of fluorinated electrocyclisation precursors in modest to good yield. Subsequent electrocyclisation afforded fluorobenzene, fluoronaphthalene and fluorophenanthrene species. The electrocyclisations were investigated computationally in an attempt to rationalise the ease/difficulty of cyclisation."],"dc:identifier":["T13938"],"dc:identifier.doi":["10.48730/0xk1-ck07"],"dc:identifier.uri":["https://stax.strath.ac.uk/concern/theses/7s75dc423"],"dc:publisher.department":["Department of Pure and Applied Chemistry"],"dc:publisher.institution":["University of Strathclyde"],"dc:title":["A novel route to fluoroarenes from trifluoroethanol"],"dc:type.qualificationlevel":["doctoral-pg"],"dc:type.qualificationname":["phd"]},"updated_at":"2026-07-24T04:45:53Z"}