{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/114100"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/114100","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"The development of Pd(II)sulfoxide-oxazoline catalyzed allylic C—H functionalizations","abstract":"Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2023-12-01","abstract_html":"Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2023-12-01","abstract_has_math":false,"creators":["Ali, Siraj Zaki"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["White, Maria C","Denmark, Scott E","Hergenrother, Paul J","Rauchfuss, Thomas B"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2022,"date_issued":"2022-04-29T21:58:38Z","date_published":"2022-04-29T21:58:38Z","updated_at":"2026-07-22T22:24:54Z","subjects":["Chemistry"],"languages":["en","eng"],"rights":["Copyright 2021 Siraj Ali"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/114100","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["White, Maria C","Denmark, Scott E","Hergenrother, Paul J","Rauchfuss, Thomas B"]},{"key":"dc:creator","label":"Author","values":["Ali, Siraj Zaki"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2022-04-29T21:58:38Z","2024-04-29T21:58:46Z","2021-12","2021-12-03"]},{"key":"dc:type","label":"Dc Type","values":["text","Thesis"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois at Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en","eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2021 Siraj Ali"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/114100"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2023-12-01","The student, Siraj Ali, accepted the attached license on 2021-12-02 at 13:32.","The student, Siraj Ali, submitted this Dissertation for approval on 2021-12-02 at 13:36.","This Dissertation was approved for publication on 2021-12-03 at 15:58.","DSpace SAF Submission Ingestion Package generated from Vireo submission #17361 on 2022-04-29 at 16:10:31","Made available in DSpace on 2022-04-29T21:58:38Z (GMT). No. of bitstreams: 4 ALI-DISSERTATION-2021.pdf: 7393062 bytes, checksum: f137d50996aff3fe3e20540ebadd94fb (MD5) CertificateOfCompletion.pdf: 122643 bytes, checksum: ea023b4fafccb64c1aa35282681066fc (MD5) LICENSE.txt: 4206 bytes, checksum: e6420aaa1b26fb531f0c56b3aa214ea6 (MD5) PROQUEST_LICENSE.txt: 4552 bytes, checksum: 87f1da545ed1126befbeb6ba96d710ba (MD5) Previous issue date: 2021-12-03","Embargo set by: Seth Robbins for item 123465 Lift date: 2024-04-29T21:58:46Z Reason: Author requested closed access (OA after 2yrs) in Vireo ETD system","Author requested closed access (OA after 2yrs) in Vireo ETD system","Limited","Pd-catalyzed allylic C—H functionalization is a powerful platform to stereoselectively and regioselectively convert terminal olefins (typically considered inert under most reaction conditions) into higher value chemical commodities. At the outset of this research program, several challenges with allylic C—H functionalization included: poor to moderate enantioselectivities in stereoselective transformations, and limited scope of functionalization partners. This thesis describes effort towards the development and application of Pd(II)/sulfoxide-oxazoline (Pd(II)/SOX) catalysis towards addressing these challenges. The first chapter outlines the development and application of Pd(II)/SOX catalysis towards the difficult challenge of asymmetric allylic C—H alkylation. Critical to this strategy was investigations into the cis-SOX ligand framework—a diastereomer of the SOX ligand which was theorized to have greater enantiocontrol around the intermediate π-allyl. This chapter describes the development and application of this system to α-nitrotetralones, a versatile precursor to amino ketones and amino alcohols. The chapter also details efforts into addressing challenging β-ketoester nucleophiles, and the elucidation of a key ligand structural feature important for enantioselectivity. The second chapter outlines the development and application of Pd(II)/SOX catalysis towards allylic C—H aminations with basic secondary amines. Intermolecular C—H amination is typically limited to doubly or singly protected nitrogen species, allowing only for protected ammonia or primary amine installation. Typically, basic amines are liable to bind tightly to the electrophilic metal catalysts for C—H cleavage and can inhibit useful reactivity. An amine quaternization strategy was applied to basic secondary amines, which allowed for a slow release of the free amine. This slow release allowed for functionalization to occur with no detrimental inhibition of the electrophilic Pd(II) center. This strategy was applied to a variety of secondary amines cores, forging pharmaceutically relevant tertiary amine products. In addition, the mild selective allylic functionalization was tolerant of numerous functionalities considered traditional electrophiles for amino functionalization. Finally, several tertiary amine drugs and drug derivatives were synthesized, demonstrating the synthetic utility of this transformation."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["The development of Pd(II)sulfoxide-oxazoline catalyzed allylic C—H functionalizations"]}]}],"canonical_facts":{"dc:contributor":["White, Maria C","Denmark, Scott E","Hergenrother, Paul J","Rauchfuss, Thomas B"],"dc:creator":["Ali, Siraj Zaki"],"dc:date":["2022-04-29T21:58:38Z","2024-04-29T21:58:46Z","2021-12","2021-12-03"],"dc:description":["Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2023-12-01","The student, Siraj Ali, accepted the attached license on 2021-12-02 at 13:32.","The student, Siraj Ali, submitted this Dissertation for approval on 2021-12-02 at 13:36.","This Dissertation was approved for publication on 2021-12-03 at 15:58.","DSpace SAF Submission Ingestion Package generated from Vireo submission #17361 on 2022-04-29 at 16:10:31","Made available in DSpace on 2022-04-29T21:58:38Z (GMT). No. of bitstreams: 4 ALI-DISSERTATION-2021.pdf: 7393062 bytes, checksum: f137d50996aff3fe3e20540ebadd94fb (MD5) CertificateOfCompletion.pdf: 122643 bytes, checksum: ea023b4fafccb64c1aa35282681066fc (MD5) LICENSE.txt: 4206 bytes, checksum: e6420aaa1b26fb531f0c56b3aa214ea6 (MD5) PROQUEST_LICENSE.txt: 4552 bytes, checksum: 87f1da545ed1126befbeb6ba96d710ba (MD5) Previous issue date: 2021-12-03","Embargo set by: Seth Robbins for item 123465 Lift date: 2024-04-29T21:58:46Z Reason: Author requested closed access (OA after 2yrs) in Vireo ETD system","Author requested closed access (OA after 2yrs) in Vireo ETD system","Limited","Pd-catalyzed allylic C—H functionalization is a powerful platform to stereoselectively and regioselectively convert terminal olefins (typically considered inert under most reaction conditions) into higher value chemical commodities. At the outset of this research program, several challenges with allylic C—H functionalization included: poor to moderate enantioselectivities in stereoselective transformations, and limited scope of functionalization partners. This thesis describes effort towards the development and application of Pd(II)/sulfoxide-oxazoline (Pd(II)/SOX) catalysis towards addressing these challenges. The first chapter outlines the development and application of Pd(II)/SOX catalysis towards the difficult challenge of asymmetric allylic C—H alkylation. Critical to this strategy was investigations into the cis-SOX ligand framework—a diastereomer of the SOX ligand which was theorized to have greater enantiocontrol around the intermediate π-allyl. This chapter describes the development and application of this system to α-nitrotetralones, a versatile precursor to amino ketones and amino alcohols. The chapter also details efforts into addressing challenging β-ketoester nucleophiles, and the elucidation of a key ligand structural feature important for enantioselectivity. The second chapter outlines the development and application of Pd(II)/SOX catalysis towards allylic C—H aminations with basic secondary amines. Intermolecular C—H amination is typically limited to doubly or singly protected nitrogen species, allowing only for protected ammonia or primary amine installation. Typically, basic amines are liable to bind tightly to the electrophilic metal catalysts for C—H cleavage and can inhibit useful reactivity. An amine quaternization strategy was applied to basic secondary amines, which allowed for a slow release of the free amine. This slow release allowed for functionalization to occur with no detrimental inhibition of the electrophilic Pd(II) center. This strategy was applied to a variety of secondary amines cores, forging pharmaceutically relevant tertiary amine products. In addition, the mild selective allylic functionalization was tolerant of numerous functionalities considered traditional electrophiles for amino functionalization. Finally, several tertiary amine drugs and drug derivatives were synthesized, demonstrating the synthetic utility of this transformation."],"dc:format":["application/pdf"],"dc:identifier":["http://hdl.handle.net/2142/114100"],"dc:language":["en","eng"],"dc:rights":["Copyright 2021 Siraj Ali"],"dc:subject":["Chemistry"],"dc:title":["The development of Pd(II)sulfoxide-oxazoline catalyzed allylic C—H functionalizations"],"dc:type":["text","Thesis"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:24:54Z"}