{"id":{"repo_id":"queens","oai_identifier":"oai:queensu.scholaris.ca:1974/28683"},"canonical_url":"https://search.dev.ndltd.org/etd/queens/oai:queensu.scholaris.ca:1974/28683","repository":{"repo_id":"queens","name":"Queens University","base_url":"https://qspace.library.queensu.ca/server/oai/request"},"display":{"title":"TRANSITION METAL CATALYZED CROSS-COUPLINGS OF ALKYL SULFONE ELECTROPHILES","abstract":"Sulfones are an important class of organic molecules that can participate in a wide variety of synthetic transformations. For this reason, they have been described as chemical chameleons. While their use as Csp2 electrophiles in cross-coupling dates to the early 1970’s, their potential as competent Csp3 electrophiles has not been recognized until recently. Our group has made significant contributions to the development of new cross-coupling methodologies utilizing alkyl sulfones as electrophiles. This thesis describes the use of alkyl sulfones as electrophiles in both nickel and palladium catalyzed cross-coupling reactions. First, we developed a nickel-catalyzed Suzuki–Miyaura cross-coupling of π-extended tertiary benzylic and allylic sulfones with arylboroxines. A variety of tertiary sulfones were reacted to afford quaternary products in good yields and we identified a unique phosphine ligand capable of promoting the challenging cross-coupling reaction. The method enabled the concise synthesis of a biologically active molecule. We then adapted and extended the nickel-catalyzed system to the cross-coupling of simple tertiary benzylic sulfones using olefins as removable directing groups. Several dialkydiarylmethanes were prepared in good yields and we revealed that the mechanism likely involves an η2-nickel coordination complex with the olefin, which facilitates oxidative addition. Following cross-coupling, the olefin could be cleaved to introduce new functionalities. Next, we developed a nickel-catalyzed Kumada cross-coupling of cyclic alkyl sulfones with aryl Grignard nucleophiles. Uniquely, the sulfinate leaving group was retained following ring-opening cross-coupling and it served as a handle for further functionalization. Overall, the methodology provided access to doubly functionalized products in a one-pot procedure. Finally, we developed a palladium-catalyzed Suzuki-Miyaura cross-coupling of α-fluorinated benzylic triflones with arylboronic acids. The method afforded a variety of mono- and difluorinated diarylmethanes and we demonstrated that both mono- and difluorinated benzylic triflones could be desulfonylated to afford the corresponding α-fluoromethylarenes. Because α-fluoromethylarenes are important substructures in pharmaceuticals and agrochemicals, we utilized our methodology to prepare several fluorinated analogues and derivatives of biologically active compounds.","abstract_html":"Sulfones are an important class of organic molecules that can participate in a wide variety of synthetic transformations. For this reason, they have been described as chemical chameleons. While their use as Csp2 electrophiles in cross-coupling dates to the early 1970’s, their potential as competent Csp3 electrophiles has not been recognized until recently. Our group has made significant contributions to the development of new cross-coupling methodologies utilizing alkyl sulfones as electrophiles. This thesis describes the use of alkyl sulfones as electrophiles in both nickel and palladium catalyzed cross-coupling reactions. First, we developed a nickel-catalyzed Suzuki–Miyaura cross-coupling of π-extended tertiary benzylic and allylic sulfones with arylboroxines. A variety of tertiary sulfones were reacted to afford quaternary products in good yields and we identified a unique phosphine ligand capable of promoting the challenging cross-coupling reaction. The method enabled the concise synthesis of a biologically active molecule. We then adapted and extended the nickel-catalyzed system to the cross-coupling of simple tertiary benzylic sulfones using olefins as removable directing groups. Several dialkydiarylmethanes were prepared in good yields and we revealed that the mechanism likely involves an η2-nickel coordination complex with the olefin, which facilitates oxidative addition. Following cross-coupling, the olefin could be cleaved to introduce new functionalities. Next, we developed a nickel-catalyzed Kumada cross-coupling of cyclic alkyl sulfones with aryl Grignard nucleophiles. Uniquely, the sulfinate leaving group was retained following ring-opening cross-coupling and it served as a handle for further functionalization. Overall, the methodology provided access to doubly functionalized products in a one-pot procedure. Finally, we developed a palladium-catalyzed Suzuki-Miyaura cross-coupling of α-fluorinated benzylic triflones with arylboronic acids. The method afforded a variety of mono- and difluorinated diarylmethanes and we demonstrated that both mono- and difluorinated benzylic triflones could be desulfonylated to afford the corresponding α-fluoromethylarenes. Because α-fluoromethylarenes are important substructures in pharmaceuticals and agrochemicals, we utilized our methodology to prepare several fluorinated analogues and derivatives of biologically active compounds.","abstract_has_math":false,"creators":["Ariki, Zachary"],"institution":null,"degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":"Chemistry","school":null,"contributors":[],"advisors":["Crudden, Cathleen"],"committee_chairs":[],"committee_members":[],"year":null,"date_issued":"","date_published":null,"updated_at":"2026-07-27T20:35:33Z","subjects":["Cross-coupling","Sulfone","Nickel"],"languages":["eng"],"rights":["CC0 1.0 Universal"],"rights_urls":["http://creativecommons.org/publicdomain/zero/1.0/"],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/1974/28683","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.department","label":"Department","values":["Chemistry"]},{"key":"dc:contributor.supervisor","label":"Supervisor","values":["Crudden, Cathleen"]},{"key":"dc:creator","label":"Author","values":["Ariki, Zachary"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2021-02-01T21:58:50Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2021-02-01T21:58:50Z"]},{"key":"dc:type","label":"Dc Type","values":["thesis"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Cross-coupling","Sulfone","Nickel"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["CC0 1.0 Universal"]},{"key":"dc:rights.uri","label":"Rights URI","values":["http://creativecommons.org/publicdomain/zero/1.0/"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://hdl.handle.net/1974/28683"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Sulfones are an important class of organic molecules that can participate in a wide variety of synthetic transformations. For this reason, they have been described as chemical chameleons. While their use as Csp2 electrophiles in cross-coupling dates to the early 1970’s, their potential as competent Csp3 electrophiles has not been recognized until recently. Our group has made significant contributions to the development of new cross-coupling methodologies utilizing alkyl sulfones as electrophiles. This thesis describes the use of alkyl sulfones as electrophiles in both nickel and palladium catalyzed cross-coupling reactions. First, we developed a nickel-catalyzed Suzuki–Miyaura cross-coupling of π-extended tertiary benzylic and allylic sulfones with arylboroxines. A variety of tertiary sulfones were reacted to afford quaternary products in good yields and we identified a unique phosphine ligand capable of promoting the challenging cross-coupling reaction. The method enabled the concise synthesis of a biologically active molecule. We then adapted and extended the nickel-catalyzed system to the cross-coupling of simple tertiary benzylic sulfones using olefins as removable directing groups. Several dialkydiarylmethanes were prepared in good yields and we revealed that the mechanism likely involves an η2-nickel coordination complex with the olefin, which facilitates oxidative addition. Following cross-coupling, the olefin could be cleaved to introduce new functionalities. Next, we developed a nickel-catalyzed Kumada cross-coupling of cyclic alkyl sulfones with aryl Grignard nucleophiles. Uniquely, the sulfinate leaving group was retained following ring-opening cross-coupling and it served as a handle for further functionalization. Overall, the methodology provided access to doubly functionalized products in a one-pot procedure. Finally, we developed a palladium-catalyzed Suzuki-Miyaura cross-coupling of α-fluorinated benzylic triflones with arylboronic acids. The method afforded a variety of mono- and difluorinated diarylmethanes and we demonstrated that both mono- and difluorinated benzylic triflones could be desulfonylated to afford the corresponding α-fluoromethylarenes. Because α-fluoromethylarenes are important substructures in pharmaceuticals and agrochemicals, we utilized our methodology to prepare several fluorinated analogues and derivatives of biologically active compounds."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["PhD"]},{"key":"dc:title","label":"Title","values":["TRANSITION METAL CATALYZED CROSS-COUPLINGS OF ALKYL SULFONE ELECTROPHILES"]}]}],"canonical_facts":{"dc:contributor.department":["Chemistry"],"dc:contributor.supervisor":["Crudden, Cathleen"],"dc:creator":["Ariki, Zachary"],"dc:date.accessioned":["2021-02-01T21:58:50Z"],"dc:date.available":["2021-02-01T21:58:50Z"],"dc:description.abstract":["Sulfones are an important class of organic molecules that can participate in a wide variety of synthetic transformations. For this reason, they have been described as chemical chameleons. While their use as Csp2 electrophiles in cross-coupling dates to the early 1970’s, their potential as competent Csp3 electrophiles has not been recognized until recently. Our group has made significant contributions to the development of new cross-coupling methodologies utilizing alkyl sulfones as electrophiles. This thesis describes the use of alkyl sulfones as electrophiles in both nickel and palladium catalyzed cross-coupling reactions. First, we developed a nickel-catalyzed Suzuki–Miyaura cross-coupling of π-extended tertiary benzylic and allylic sulfones with arylboroxines. A variety of tertiary sulfones were reacted to afford quaternary products in good yields and we identified a unique phosphine ligand capable of promoting the challenging cross-coupling reaction. The method enabled the concise synthesis of a biologically active molecule. We then adapted and extended the nickel-catalyzed system to the cross-coupling of simple tertiary benzylic sulfones using olefins as removable directing groups. Several dialkydiarylmethanes were prepared in good yields and we revealed that the mechanism likely involves an η2-nickel coordination complex with the olefin, which facilitates oxidative addition. Following cross-coupling, the olefin could be cleaved to introduce new functionalities. Next, we developed a nickel-catalyzed Kumada cross-coupling of cyclic alkyl sulfones with aryl Grignard nucleophiles. Uniquely, the sulfinate leaving group was retained following ring-opening cross-coupling and it served as a handle for further functionalization. Overall, the methodology provided access to doubly functionalized products in a one-pot procedure. Finally, we developed a palladium-catalyzed Suzuki-Miyaura cross-coupling of α-fluorinated benzylic triflones with arylboronic acids. The method afforded a variety of mono- and difluorinated diarylmethanes and we demonstrated that both mono- and difluorinated benzylic triflones could be desulfonylated to afford the corresponding α-fluoromethylarenes. Because α-fluoromethylarenes are important substructures in pharmaceuticals and agrochemicals, we utilized our methodology to prepare several fluorinated analogues and derivatives of biologically active compounds."],"dc:description.degree":["PhD"],"dc:identifier.uri":["http://hdl.handle.net/1974/28683"],"dc:language.iso":["eng"],"dc:rights":["CC0 1.0 Universal"],"dc:rights.uri":["http://creativecommons.org/publicdomain/zero/1.0/"],"dc:subject":["Cross-coupling","Sulfone","Nickel"],"dc:title":["TRANSITION METAL CATALYZED CROSS-COUPLINGS OF ALKYL SULFONE ELECTROPHILES"],"dc:type":["thesis"]},"updated_at":"2026-07-27T20:35:33Z"}