{"id":{"repo_id":"toronto-retro","oai_identifier":"oai:utoronto.scholaris.ca:1807/142658"},"canonical_url":"https://search.dev.ndltd.org/etd/toronto-retro/oai:utoronto.scholaris.ca:1807/142658","repository":{"repo_id":"toronto-retro","name":"University of Toronto","base_url":"https://utoronto.scholaris.ca/server/oai/request"},"display":{"title":"Electrophilic Cyanation of Alkenyl Tosylates, Ketones and Amines using Disubstituted Malononitriles","abstract":"This thesis describes new methods for the synthesis of alkenyl nitriles, β-ketonitriles, andcyanamides using various disubstituted malononitriles as electrophilic cyanation reagents. These approaches may be of interest to workers attempting to access compounds of those types. Chapter 1 provides a brief overview of the thesis topics and compares nucleophilic to electrophilic cyanation. Chapter 2 describes a novel method for the construction of alkenyl nitriles from alkenyl tosylates using disubstituted malononitriles as electrophilic cyanating reagents under reductive nickel catalysis. Chapter 3 describes a novel method for the synthesis of β-ketonitriles from ketones and disubstituted malononitriles under basic conditions. Several β-ketoenamines were found to be produced using similar conditions, and their synthesis is also elaborated. Chapter 4 describes continued efforts related to the synthesis cyanamides using disubstituted malononitriles under basic conditions. A novel ortho-functionalization of the cyanating reagent byproduct was observed during reaction optimization.","abstract_html":"This thesis describes new methods for the synthesis of alkenyl nitriles, β-ketonitriles, andcyanamides using various disubstituted malononitriles as electrophilic cyanation reagents. These approaches may be of interest to workers attempting to access compounds of those types. Chapter 1 provides a brief overview of the thesis topics and compares nucleophilic to electrophilic cyanation. Chapter 2 describes a novel method for the construction of alkenyl nitriles from alkenyl tosylates using disubstituted malononitriles as electrophilic cyanating reagents under reductive nickel catalysis. Chapter 3 describes a novel method for the synthesis of β-ketonitriles from ketones and disubstituted malononitriles under basic conditions. Several β-ketoenamines were found to be produced using similar conditions, and their synthesis is also elaborated. Chapter 4 describes continued efforts related to the synthesis cyanamides using disubstituted malononitriles under basic conditions. A novel ortho-functionalization of the cyanating reagent byproduct was observed during reaction optimization.","abstract_has_math":false,"creators":["Graham, Joshua Morgan"],"institution":null,"degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":"Chemistry","school":null,"contributors":[],"advisors":["Rousseaux, Sophie"],"committee_chairs":[],"committee_members":[],"year":2025,"date_issued":"2025-03","date_published":"2025-03","updated_at":"2026-07-27T21:27:58Z","subjects":[],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/1807/142658","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Rousseaux, Sophie"]},{"key":"dc:contributor.department","label":"Department","values":["Chemistry"]},{"key":"dc:creator","label":"Author","values":["Graham, Joshua Morgan"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2025-03"]},{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2025-04-18T15:08:54Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2025-04-18T15:08:54Z"]},{"key":"dc:date.issued","label":"Date","values":["2025-03"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://hdl.handle.net/1807/142658"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["This thesis describes new methods for the synthesis of alkenyl nitriles, β-ketonitriles, andcyanamides using various disubstituted malononitriles as electrophilic cyanation reagents. These approaches may be of interest to workers attempting to access compounds of those types. Chapter 1 provides a brief overview of the thesis topics and compares nucleophilic to electrophilic cyanation. Chapter 2 describes a novel method for the construction of alkenyl nitriles from alkenyl tosylates using disubstituted malononitriles as electrophilic cyanating reagents under reductive nickel catalysis. Chapter 3 describes a novel method for the synthesis of β-ketonitriles from ketones and disubstituted malononitriles under basic conditions. Several β-ketoenamines were found to be produced using similar conditions, and their synthesis is also elaborated. Chapter 4 describes continued efforts related to the synthesis cyanamides using disubstituted malononitriles under basic conditions. A novel ortho-functionalization of the cyanating reagent byproduct was observed during reaction optimization."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["Ph.D."]},{"key":"dc:title","label":"Title","values":["Electrophilic Cyanation of Alkenyl Tosylates, Ketones and Amines using Disubstituted Malononitriles"]}]}],"canonical_facts":{"dc:contributor.advisor":["Rousseaux, Sophie"],"dc:contributor.department":["Chemistry"],"dc:creator":["Graham, Joshua Morgan"],"dc:date":["2025-03"],"dc:date.accessioned":["2025-04-18T15:08:54Z"],"dc:date.available":["2025-04-18T15:08:54Z"],"dc:date.issued":["2025-03"],"dc:description.abstract":["This thesis describes new methods for the synthesis of alkenyl nitriles, β-ketonitriles, andcyanamides using various disubstituted malononitriles as electrophilic cyanation reagents. These approaches may be of interest to workers attempting to access compounds of those types. Chapter 1 provides a brief overview of the thesis topics and compares nucleophilic to electrophilic cyanation. Chapter 2 describes a novel method for the construction of alkenyl nitriles from alkenyl tosylates using disubstituted malononitriles as electrophilic cyanating reagents under reductive nickel catalysis. Chapter 3 describes a novel method for the synthesis of β-ketonitriles from ketones and disubstituted malononitriles under basic conditions. Several β-ketoenamines were found to be produced using similar conditions, and their synthesis is also elaborated. Chapter 4 describes continued efforts related to the synthesis cyanamides using disubstituted malononitriles under basic conditions. A novel ortho-functionalization of the cyanating reagent byproduct was observed during reaction optimization."],"dc:description.degree":["Ph.D."],"dc:identifier.uri":["https://hdl.handle.net/1807/142658"],"dc:title":["Electrophilic Cyanation of Alkenyl Tosylates, Ketones and Amines using Disubstituted Malononitriles"],"dc:type":["Thesis"]},"updated_at":"2026-07-27T21:27:58Z"}