{"id":{"repo_id":"cambridge","oai_identifier":"oai:www.repository.cam.ac.uk:1810/360862"},"canonical_url":"https://search.dev.ndltd.org/etd/cambridge/oai:www.repository.cam.ac.uk:1810/360862","repository":{"repo_id":"cambridge","name":"Cambridge University","base_url":"https://api.repository.cam.ac.uk/server/oai/request"},"display":{"title":"Photochemical Methods for the Construction of C-C and C-X Bonds","abstract":"This thesis encompasses photochemical methods for the construction of C-C and C-X bonds. Following an introduction on the challenges with photochemistry, early work in photoredox catalysis and the application of continuous processing for photochemical reactions are three research chapters. Chapter 2 discloses the development of a photoredox-catalysed dehydrogenative cross-coupling reaction between aldehydes and alkylarenes in continuous flow. In the process, the reaction was adapted to a flow set-up, further optimised and expanded to prepare a range of α-aryl ketones including drug derivatives. Furthermore, the application of flow reactors towards multi-gram scale-up was investigated and in doing so, a previously unreported method to recycle the iridium photocatalyst was established. Chapter 3 contains a new method to prepare β-spiropyrrolidines using visible-light-driven photocatalysis. By adapting and re-optimising a photocatalytic pyrrolidine ring forming reaction developed within the Ley group, a range of β-spiropyrrolidines were prepared. In addition, the reaction was shown to be well-suited to a flow set-up and was successfully executed on a decagram scale. The products were then derivatised at the halomethyl substituent formed on the pyrrolidine ring. Finally, a brief investigation into the preparation of piperidine rings with this strategy was made. Chapter 4 investigates new methods to access sulfonyl compounds via sulfinate salts. This began with the development of a photoredox-catalysed sulfinate preparation using a previously unexplored piperidine-SO2 surrogate. With this reaction, a variety of alkyl and aryl sulfones were prepared by quenching of the generated sulfinates, including drug derivatives. Following this, a pilot study into a new nitro-sulfinate reductive coupling strategy was conducted to access sulfonamides directly from sulfinates. In doing so, two sets of general conditions were established that enabled access to a selection of N-heteroaryl sulfonamides, that were previously inaccessible with alternative reductive coupling methods.","abstract_html":"This thesis encompasses photochemical methods for the construction of C-C and C-X bonds. Following an introduction on the challenges with photochemistry, early work in photoredox catalysis and the application of continuous processing for photochemical reactions are three research chapters. Chapter 2 discloses the development of a photoredox-catalysed dehydrogenative cross-coupling reaction between aldehydes and alkylarenes in continuous flow. In the process, the reaction was adapted to a flow set-up, further optimised and expanded to prepare a range of α-aryl ketones including drug derivatives. Furthermore, the application of flow reactors towards multi-gram scale-up was investigated and in doing so, a previously unreported method to recycle the iridium photocatalyst was established. Chapter 3 contains a new method to prepare β-spiropyrrolidines using visible-light-driven photocatalysis. By adapting and re-optimising a photocatalytic pyrrolidine ring forming reaction developed within the Ley group, a range of β-spiropyrrolidines were prepared. In addition, the reaction was shown to be well-suited to a flow set-up and was successfully executed on a decagram scale. The products were then derivatised at the halomethyl substituent formed on the pyrrolidine ring. Finally, a brief investigation into the preparation of piperidine rings with this strategy was made. Chapter 4 investigates new methods to access sulfonyl compounds via sulfinate salts. This began with the development of a photoredox-catalysed sulfinate preparation using a previously unexplored piperidine-SO2 surrogate. With this reaction, a variety of alkyl and aryl sulfones were prepared by quenching of the generated sulfinates, including drug derivatives. Following this, a pilot study into a new nitro-sulfinate reductive coupling strategy was conducted to access sulfonamides directly from sulfinates. In doing so, two sets of general conditions were established that enabled access to a selection of N-heteroaryl sulfonamides, that were previously inaccessible with alternative reductive coupling methods.","abstract_has_math":false,"creators":["Griffiths, Oliver"],"institution":"University of Cambridge","degree_name":"Doctor of Philosophy (PhD)","degree_level":"Doctoral","degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Ley, Steven V","Spring, David"],"committee_chairs":[],"committee_members":[],"year":2023,"date_issued":"2023-08-02","date_published":"2023-08-02","updated_at":"2026-07-22T22:24:04Z","subjects":["Cross-coupling","Flow chemistry","Photocatalysis","Photochemistry","Photoredox catalysis","Spirocycles","Sulfonamides","Sulfones"],"languages":["eng"],"rights":[],"rights_urls":["https://apollo8-f-pro.lib.cam.ac.uk/bitstreams/62fd0060-bd61-40fa-aa4e-83981127ba0a/download","https://www.rioxx.net/licenses/all-rights-reserved/"],"identifier_entries":[{"key":"dc:creator.authoridentifier","label":"Author Identifier","values":["0000000339549343"],"render_values":[{"text":"0000-0003-3954-9343","href":"https://orcid.org/0000-0003-3954-9343","code":true}]}]},"links":{"outbound_url":"https://doi.org/10.17863/CAM.104082","outbound_label":"DOI","outbound_source":"dc:identifier.doi"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Ley, Steven V","Spring, David"]},{"key":"dc:creator","label":"Author","values":["Griffiths, Oliver"]},{"key":"dc:creator.authoridentifier","label":"Author Identifier","values":["0000000339549343"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.issued","label":"Date","values":["2023-08-02"]},{"key":"dc:publisher.institution","label":"Dc Publisher Institution","values":["University of Cambridge"]},{"key":"dc:relation.isreferencedby.uri","label":"Dc Relation Isreferencedby URI","values":["https://www.repository.cam.ac.uk/handle/1810/360862"]},{"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":["Doctor of Philosophy (PhD)"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Cross-coupling","Flow chemistry","Photocatalysis","Photochemistry","Photoredox catalysis","Spirocycles","Sulfonamides","Sulfones"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["https://apollo8-f-pro.lib.cam.ac.uk/bitstreams/62fd0060-bd61-40fa-aa4e-83981127ba0a/download","https://www.rioxx.net/licenses/all-rights-reserved/"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.doi","label":"DOI","values":["https://doi.org/10.17863/CAM.104082"]},{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://apollo8-f-pro.lib.cam.ac.uk/bitstreams/2df4101d-395f-40f9-adce-4dfd550a2476/download"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["This thesis encompasses photochemical methods for the construction of C-C and C-X bonds. 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In addition, the reaction was shown to be well-suited to a flow set-up and was successfully executed on a decagram scale. The products were then derivatised at the halomethyl substituent formed on the pyrrolidine ring. Finally, a brief investigation into the preparation of piperidine rings with this strategy was made. Chapter 4 investigates new methods to access sulfonyl compounds via sulfinate salts. This began with the development of a photoredox-catalysed sulfinate preparation using a previously unexplored piperidine-SO2 surrogate. With this reaction, a variety of alkyl and aryl sulfones were prepared by quenching of the generated sulfinates, including drug derivatives. Following this, a pilot study into a new nitro-sulfinate reductive coupling strategy was conducted to access sulfonamides directly from sulfinates. 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Finally, a brief investigation into the preparation of piperidine rings with this strategy was made. Chapter 4 investigates new methods to access sulfonyl compounds via sulfinate salts. This began with the development of a photoredox-catalysed sulfinate preparation using a previously unexplored piperidine-SO2 surrogate. With this reaction, a variety of alkyl and aryl sulfones were prepared by quenching of the generated sulfinates, including drug derivatives. Following this, a pilot study into a new nitro-sulfinate reductive coupling strategy was conducted to access sulfonamides directly from sulfinates. 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