{"id":{"repo_id":"strathclyde","oai_identifier":"oai:strathclyde:3f462541v"},"canonical_url":"https://search.dev.ndltd.org/etd/strathclyde/oai:strathclyde:3f462541v","repository":{"repo_id":"strathclyde","name":"University of Strathclyde","base_url":"https://stax.strath.ac.uk/catalog/oai"},"display":{"title":"Broadening the scope of reactivity for neutral organic electron donors","abstract":"Reduction and oxidation of functional groups are some of the fundamental transformations in inorganic and organic synthesis. Compound A has been shown to be a powerful neutral organic electron donor capable of the reductive bond cleavage of various σ-bonds. Photoactivation of donor A (to A*) has been discovered to increase the reducing power of the species therefore allowing the reduction of less activated bonds and this body of work explores examples such as: carbon-nitrogen bonds of benzyl sulfonamides and aniline derivatives; carbon-oxygen bonds of benzyl ethers, esters and carbamates; carbon-carbon bonds of benzylated carbon acids; carbon-sulfur bonds of aryl methyl sulfides, oxygen-sulfur bonds of aryl and alkyl triflate esters; and nitrogen-sulfur bonds of tosylamides and activated mesylamides. A series of nitrogen-containing substrates, B-E, was investigated for their reactivity with the photoactivated donor A*. The results of these experiments were the high-yielding carbon nitrogen bond scissions, the details of which are reported herein including a mechanistic discussion and supporting evidence. Likewise, aryl methyl sulfides F and H were cleaved in good yield with the photoactivated donor A. A number of related results demonstrate the scope of the chemistry and provide insights into the mechanism of the process. Careful analysis of the reaction by-products from the above investigations has also allowed the elucidation of the structures of a number of compounds A++, J, K, L, derived from donor A under the reaction conditions. The mechanism of formation of these species and the insight offered into donor reactivity are discussed.","abstract_html":"Reduction and oxidation of functional groups are some of the fundamental transformations in inorganic and organic synthesis. Compound A has been shown to be a powerful neutral organic electron donor capable of the reductive bond cleavage of various σ-bonds. Photoactivation of donor A (to A*) has been discovered to increase the reducing power of the species therefore allowing the reduction of less activated bonds and this body of work explores examples such as: carbon-nitrogen bonds of benzyl sulfonamides and aniline derivatives; carbon-oxygen bonds of benzyl ethers, esters and carbamates; carbon-carbon bonds of benzylated carbon acids; carbon-sulfur bonds of aryl methyl sulfides, oxygen-sulfur bonds of aryl and alkyl triflate esters; and nitrogen-sulfur bonds of tosylamides and activated mesylamides. A series of nitrogen-containing substrates, B-E, was investigated for their reactivity with the photoactivated donor A*. The results of these experiments were the high-yielding carbon nitrogen bond scissions, the details of which are reported herein including a mechanistic discussion and supporting evidence. Likewise, aryl methyl sulfides F and H were cleaved in good yield with the photoactivated donor A. A number of related results demonstrate the scope of the chemistry and provide insights into the mechanism of the process. Careful analysis of the reaction by-products from the above investigations has also allowed the elucidation of the structures of a number of compounds A++, J, K, L, derived from donor A under the reaction conditions. The mechanism of formation of these species and the insight offered into donor reactivity are discussed.","abstract_has_math":false,"creators":["O'Sullivan, Steven"],"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":"2026-07-24T04:42:40Z","subjects":[],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier.doi","label":"DOI","values":["10.48730/hq6m-rp29"],"render_values":[{"text":"10.48730/hq6m-rp29","href":"https://doi.org/10.48730/hq6m-rp29","code":true}]},{"key":"dc:identifier","label":"Identifier","values":["T13835"],"render_values":[{"text":"T13835","href":null,"code":true}]}]},"links":{"outbound_url":"https://stax.strath.ac.uk/concern/theses/3f462541v","outbound_label":"Repository record","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["O'Sullivan, Steven"]}]},{"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","WestCHEM"]},{"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":["T13835"]},{"key":"dc:identifier.doi","label":"DOI","values":["10.48730/hq6m-rp29"]},{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://stax.strath.ac.uk/concern/theses/3f462541v"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Reduction and oxidation of functional groups are some of the fundamental transformations in inorganic and organic synthesis. Compound A has been shown to be a powerful neutral organic electron donor capable of the reductive bond cleavage of various σ-bonds. Photoactivation of donor A (to A*) has been discovered to increase the reducing power of the species therefore allowing the reduction of less activated bonds and this body of work explores examples such as: carbon-nitrogen bonds of benzyl sulfonamides and aniline derivatives; carbon-oxygen bonds of benzyl ethers, esters and carbamates; carbon-carbon bonds of benzylated carbon acids; carbon-sulfur bonds of aryl methyl sulfides, oxygen-sulfur bonds of aryl and alkyl triflate esters; and nitrogen-sulfur bonds of tosylamides and activated mesylamides. A series of nitrogen-containing substrates, B-E, was investigated for their reactivity with the photoactivated donor A*. The results of these experiments were the high-yielding carbon nitrogen bond scissions, the details of which are reported herein including a mechanistic discussion and supporting evidence. Likewise, aryl methyl sulfides F and H were cleaved in good yield with the photoactivated donor A. A number of related results demonstrate the scope of the chemistry and provide insights into the mechanism of the process. Careful analysis of the reaction by-products from the above investigations has also allowed the elucidation of the structures of a number of compounds A++, J, K, L, derived from donor A under the reaction conditions. The mechanism of formation of these species and the insight offered into donor reactivity are discussed."]},{"key":"dc:description.abstract","label":"Abstract","values":["Reduction and oxidation of functional groups are some of the fundamental transformations in inorganic and organic synthesis. Compound A has been shown to be a powerful neutral organic electron donor capable of the reductive bond cleavage of various σ-bonds. Photoactivation of donor A (to A*) has been discovered to increase the reducing power of the species therefore allowing the reduction of less activated bonds and this body of work explores examples such as: carbon-nitrogen bonds of benzyl sulfonamides and aniline derivatives; carbon-oxygen bonds of benzyl ethers, esters and carbamates; carbon-carbon bonds of benzylated carbon acids; carbon-sulfur bonds of aryl methyl sulfides, oxygen-sulfur bonds of aryl and alkyl triflate esters; and nitrogen-sulfur bonds of tosylamides and activated mesylamides. A series of nitrogen-containing substrates, B-E, was investigated for their reactivity with the photoactivated donor A*. The results of these experiments were the high-yielding carbon nitrogen bond scissions, the details of which are reported herein including a mechanistic discussion and supporting evidence. Likewise, aryl methyl sulfides F and H were cleaved in good yield with the photoactivated donor A. A number of related results demonstrate the scope of the chemistry and provide insights into the mechanism of the process. Careful analysis of the reaction by-products from the above investigations has also allowed the elucidation of the structures of a number of compounds A++, J, K, L, derived from donor A under the reaction conditions. The mechanism of formation of these species and the insight offered into donor reactivity are discussed."]},{"key":"dc:title","label":"Title","values":["Broadening the scope of reactivity for neutral organic electron donors"]}]}],"canonical_facts":{"dc:creator":["O'Sullivan, Steven"],"dc:date":["2014"],"dc:date.issued":["2014"],"dc:description":["Reduction and oxidation of functional groups are some of the fundamental transformations in inorganic and organic synthesis. Compound A has been shown to be a powerful neutral organic electron donor capable of the reductive bond cleavage of various σ-bonds. Photoactivation of donor A (to A*) has been discovered to increase the reducing power of the species therefore allowing the reduction of less activated bonds and this body of work explores examples such as: carbon-nitrogen bonds of benzyl sulfonamides and aniline derivatives; carbon-oxygen bonds of benzyl ethers, esters and carbamates; carbon-carbon bonds of benzylated carbon acids; carbon-sulfur bonds of aryl methyl sulfides, oxygen-sulfur bonds of aryl and alkyl triflate esters; and nitrogen-sulfur bonds of tosylamides and activated mesylamides. A series of nitrogen-containing substrates, B-E, was investigated for their reactivity with the photoactivated donor A*. The results of these experiments were the high-yielding carbon nitrogen bond scissions, the details of which are reported herein including a mechanistic discussion and supporting evidence. Likewise, aryl methyl sulfides F and H were cleaved in good yield with the photoactivated donor A. A number of related results demonstrate the scope of the chemistry and provide insights into the mechanism of the process. Careful analysis of the reaction by-products from the above investigations has also allowed the elucidation of the structures of a number of compounds A++, J, K, L, derived from donor A under the reaction conditions. The mechanism of formation of these species and the insight offered into donor reactivity are discussed."],"dc:description.abstract":["Reduction and oxidation of functional groups are some of the fundamental transformations in inorganic and organic synthesis. Compound A has been shown to be a powerful neutral organic electron donor capable of the reductive bond cleavage of various σ-bonds. Photoactivation of donor A (to A*) has been discovered to increase the reducing power of the species therefore allowing the reduction of less activated bonds and this body of work explores examples such as: carbon-nitrogen bonds of benzyl sulfonamides and aniline derivatives; carbon-oxygen bonds of benzyl ethers, esters and carbamates; carbon-carbon bonds of benzylated carbon acids; carbon-sulfur bonds of aryl methyl sulfides, oxygen-sulfur bonds of aryl and alkyl triflate esters; and nitrogen-sulfur bonds of tosylamides and activated mesylamides. A series of nitrogen-containing substrates, B-E, was investigated for their reactivity with the photoactivated donor A*. The results of these experiments were the high-yielding carbon nitrogen bond scissions, the details of which are reported herein including a mechanistic discussion and supporting evidence. Likewise, aryl methyl sulfides F and H were cleaved in good yield with the photoactivated donor A. A number of related results demonstrate the scope of the chemistry and provide insights into the mechanism of the process. Careful analysis of the reaction by-products from the above investigations has also allowed the elucidation of the structures of a number of compounds A++, J, K, L, derived from donor A under the reaction conditions. The mechanism of formation of these species and the insight offered into donor reactivity are discussed."],"dc:identifier":["T13835"],"dc:identifier.doi":["10.48730/hq6m-rp29"],"dc:identifier.uri":["https://stax.strath.ac.uk/concern/theses/3f462541v"],"dc:publisher.department":["Department of Pure and Applied Chemistry","WestCHEM"],"dc:publisher.institution":["University of Strathclyde"],"dc:title":["Broadening the scope of reactivity for neutral organic electron donors"],"dc:type.qualificationlevel":["doctoral-pg"],"dc:type.qualificationname":["phd"]},"updated_at":"2026-07-24T04:42:40Z"}