{"id":{"repo_id":"birmingham","oai_identifier":"oai:etheses.bham.ac.uk:98"},"canonical_url":"https://search.dev.ndltd.org/etd/birmingham/oai:etheses.bham.ac.uk:98","repository":{"repo_id":"birmingham","name":"University of Birmingham","base_url":"https://etheses.bham.ac.uk/cgi/oai2"},"display":{"title":"Generating structural diversity in \\(\\alpha\\)[alpha],\\(\\alpha\\)[alpha]-difluoromethyl ketones","abstract":"This thesis describes attempts to use palladium-catalysed cross-coupling methodology in the synthesis of \\(\\alpha\\),\\(\\alpha\\)-difluoroketones contained within a diverse array of molecular motifs. 1-(\\(N\\),\\(N\\)-Diethylcarbamoyloxy)-2,2-difluoro-1-(tributylstannyl)ethene undergoes Stille cross coupling with a variety of aryl, heteroaryl, vinyl and allyl organic electrophiles. Conditions, which promote in situ transmetallation to a more reactive copper intermediate, were essential for obtaining significant quantities of product. 1-(\\(N\\),\\(N\\)-Diethylcarbamoyloxy)-2,2-difluoro-1-iodoethene also underwent coupling with a range of aryl, heteroaryl and vinyl stannanes. Due to the difficulties with cleavage of this protecting group, the synthesis and potential application of an \\(N\\)-ethyl-\\(N\\)-(2-methylallyl)carbamate has been studied. A 2-methoxyethoxymethyl (MEM) protecting group strategy proved very successful for the synthesis of a range of difluoromethyl aryl ketones. Two consecutive coupling reactions were possible from a difluoroenol stannane, in which coupling of initial styrene products bearing a triflate group afforded a range of biarylethenes. Cleavage occurred under mild electrophilic conditions with protic, halogen, sulfur and carbon electrophiles. Diene products have been tested for reactivity in Sharpless Asymmetric Dihydroxylation. A 1,4-diene has been converted through to a fluorinated analogue of a dideoxyxylulose. A 1,3-diene has been successfully converted through to a difluorodeoxyxylulose of current interest. Key points involve regioselective and highly enantioselective dihydroxylation of the non-fluorinated olefin. Application of a special protecting group for the allylic alcohol was essential, as was control of the pH of the reaction medium.","abstract_html":"This thesis describes attempts to use palladium-catalysed cross-coupling methodology in the synthesis of <span class=\"etd-inline-math\">&alpha;</span>,<span class=\"etd-inline-math\">&alpha;</span>-difluoroketones contained within a diverse array of molecular motifs. 1-(\\(N\\),\\(N\\)-Diethylcarbamoyloxy)-2,2-difluoro-1-(tributylstannyl)ethene undergoes Stille cross coupling with a variety of aryl, heteroaryl, vinyl and allyl organic electrophiles. Conditions, which promote in situ transmetallation to a more reactive copper intermediate, were essential for obtaining significant quantities of product. 1-(\\(N\\),\\(N\\)-Diethylcarbamoyloxy)-2,2-difluoro-1-iodoethene also underwent coupling with a range of aryl, heteroaryl and vinyl stannanes. Due to the difficulties with cleavage of this protecting group, the synthesis and potential application of an \\(N\\)-ethyl-\\(N\\)-(2-methylallyl)carbamate has been studied. A 2-methoxyethoxymethyl (MEM) protecting group strategy proved very successful for the synthesis of a range of difluoromethyl aryl ketones. Two consecutive coupling reactions were possible from a difluoroenol stannane, in which coupling of initial styrene products bearing a triflate group afforded a range of biarylethenes. Cleavage occurred under mild electrophilic conditions with protic, halogen, sulfur and carbon electrophiles. Diene products have been tested for reactivity in Sharpless Asymmetric Dihydroxylation. A 1,4-diene has been converted through to a fluorinated analogue of a dideoxyxylulose. A 1,3-diene has been successfully converted through to a difluorodeoxyxylulose of current interest. Key points involve regioselective and highly enantioselective dihydroxylation of the non-fluorinated olefin. Application of a special protecting group for the allylic alcohol was essential, as was control of the pH of the reaction medium.","abstract_has_math":true,"creators":["Fullbrook, Jeremy Jon"],"institution":"University of Birmingham","degree_name":"d_ph","degree_level":"d_ph","degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2003,"date_issued":"2003-07","date_published":"2003-07","updated_at":"2026-07-24T01:10:41Z","subjects":["QD Chemistry"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://etheses.bham.ac.uk//id/eprint/98/2/Decl_IS_Fullbrook02PhD.jpg","outbound_label":"Repository record","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.sponsor","label":"Sponsor","values":["na"]},{"key":"dc:creator","label":"Author","values":["Fullbrook, Jeremy Jon"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2003-07-21"]},{"key":"dc:date.issued","label":"Date","values":["2003-07"]},{"key":"dc:publisher.department","label":"Dc Publisher Department","values":["School of Chemical Sciences","School of Chemistry"]},{"key":"dc:publisher.institution","label":"Dc Publisher Institution","values":["University of Birmingham"]},{"key":"dc:relation.isreferencedby","label":"Dc Relation Isreferencedby","values":["http://etheses.bham.ac.uk//id/eprint/98/"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"dc:type.qualificationlevel","label":"Dc Type Qualificationlevel","values":["d_ph"]},{"key":"dc:type.qualificationname","label":"Dc Type Qualificationname","values":["d_ph"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["QD Chemistry"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://etheses.bham.ac.uk//id/eprint/98/1/Fullbrook02PhDwithAddenda.pdf","http://etheses.bham.ac.uk//id/eprint/98/2/Decl_IS_Fullbrook02PhD.jpg"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["This thesis describes attempts to use palladium-catalysed cross-coupling methodology in the synthesis of \\(\\alpha\\),\\(\\alpha\\)-difluoroketones contained within a diverse array of molecular motifs. 1-(\\(N\\),\\(N\\)-Diethylcarbamoyloxy)-2,2-difluoro-1-(tributylstannyl)ethene undergoes Stille cross coupling with a variety of aryl, heteroaryl, vinyl and allyl organic electrophiles. Conditions, which promote in situ transmetallation to a more reactive copper intermediate, were essential for obtaining significant quantities of product. 1-(\\(N\\),\\(N\\)-Diethylcarbamoyloxy)-2,2-difluoro-1-iodoethene also underwent coupling with a range of aryl, heteroaryl and vinyl stannanes. Due to the difficulties with cleavage of this protecting group, the synthesis and potential application of an \\(N\\)-ethyl-\\(N\\)-(2-methylallyl)carbamate has been studied. A 2-methoxyethoxymethyl (MEM) protecting group strategy proved very successful for the synthesis of a range of difluoromethyl aryl ketones. Two consecutive coupling reactions were possible from a difluoroenol stannane, in which coupling of initial styrene products bearing a triflate group afforded a range of biarylethenes. Cleavage occurred under mild electrophilic conditions with protic, halogen, sulfur and carbon electrophiles. Diene products have been tested for reactivity in Sharpless Asymmetric Dihydroxylation. A 1,4-diene has been converted through to a fluorinated analogue of a dideoxyxylulose. A 1,3-diene has been successfully converted through to a difluorodeoxyxylulose of current interest. Key points involve regioselective and highly enantioselective dihydroxylation of the non-fluorinated olefin. Application of a special protecting group for the allylic alcohol was essential, as was control of the pH of the reaction medium."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf","image/jpeg"]},{"key":"dc:title","label":"Title","values":["Generating structural diversity in \\(\\alpha\\)[alpha],\\(\\alpha\\)[alpha]-difluoromethyl ketones"]}]}],"canonical_facts":{"dc:contributor.sponsor":["na"],"dc:creator":["Fullbrook, Jeremy Jon"],"dc:date":["2003-07-21"],"dc:date.issued":["2003-07"],"dc:description.abstract":["This thesis describes attempts to use palladium-catalysed cross-coupling methodology in the synthesis of \\(\\alpha\\),\\(\\alpha\\)-difluoroketones contained within a diverse array of molecular motifs. 1-(\\(N\\),\\(N\\)-Diethylcarbamoyloxy)-2,2-difluoro-1-(tributylstannyl)ethene undergoes Stille cross coupling with a variety of aryl, heteroaryl, vinyl and allyl organic electrophiles. Conditions, which promote in situ transmetallation to a more reactive copper intermediate, were essential for obtaining significant quantities of product. 1-(\\(N\\),\\(N\\)-Diethylcarbamoyloxy)-2,2-difluoro-1-iodoethene also underwent coupling with a range of aryl, heteroaryl and vinyl stannanes. Due to the difficulties with cleavage of this protecting group, the synthesis and potential application of an \\(N\\)-ethyl-\\(N\\)-(2-methylallyl)carbamate has been studied. A 2-methoxyethoxymethyl (MEM) protecting group strategy proved very successful for the synthesis of a range of difluoromethyl aryl ketones. Two consecutive coupling reactions were possible from a difluoroenol stannane, in which coupling of initial styrene products bearing a triflate group afforded a range of biarylethenes. Cleavage occurred under mild electrophilic conditions with protic, halogen, sulfur and carbon electrophiles. Diene products have been tested for reactivity in Sharpless Asymmetric Dihydroxylation. A 1,4-diene has been converted through to a fluorinated analogue of a dideoxyxylulose. A 1,3-diene has been successfully converted through to a difluorodeoxyxylulose of current interest. Key points involve regioselective and highly enantioselective dihydroxylation of the non-fluorinated olefin. Application of a special protecting group for the allylic alcohol was essential, as was control of the pH of the reaction medium."],"dc:format":["application/pdf","image/jpeg"],"dc:identifier.uri":["http://etheses.bham.ac.uk//id/eprint/98/1/Fullbrook02PhDwithAddenda.pdf","http://etheses.bham.ac.uk//id/eprint/98/2/Decl_IS_Fullbrook02PhD.jpg"],"dc:publisher.department":["School of Chemical Sciences","School of Chemistry"],"dc:publisher.institution":["University of Birmingham"],"dc:relation.isreferencedby":["http://etheses.bham.ac.uk//id/eprint/98/"],"dc:subject":["QD Chemistry"],"dc:title":["Generating structural diversity in \\(\\alpha\\)[alpha],\\(\\alpha\\)[alpha]-difluoromethyl ketones"],"dc:type":["Thesis"],"dc:type.qualificationlevel":["d_ph"],"dc:type.qualificationname":["d_ph"]},"updated_at":"2026-07-24T01:10:41Z"}