{"id":{"repo_id":"york","oai_identifier":"oai:yorkspace.library.yorku.ca:10315/32194"},"canonical_url":"https://search.dev.ndltd.org/etd/york/oai:yorkspace.library.yorku.ca:10315/32194","repository":{"repo_id":"york","name":"York University","base_url":"https://yorkspace.library.yorku.ca/oai/request"},"display":{"title":"Part I: Mechanistic Insight in Alkyl-Alkyl and Aryl-Aryl Negishi Cross-Coupling Part II: Large Scale Synthesis of NHC Precursors: 2,6-DI(3-Pentyl) Aniline and 2,6-DI (4-Heptyl) Aniline","abstract":"Part I: An efficient method for alkyl-alkyl Negishi cross-coupling reaction of unactivated primary alkyl halides with higher-order zincate species (synthesized from dialkylzinc and a non-coordinating halide salt in situ) using Pd-PEPPSI-IPent (Pyridine-Enhanced Pre-catalyst Preparation Stabilization and Initiation) pre-catalyst has been developed. The method requires no additive (such as LiX) or use of a polar co-solvent (such as THF/DMI) and reactions proceed in THF solvent alone. The transmetalating species in alkyl-alkyl Negishi cross-coupling has been identified and the catalytic cycle has been amended to include the formation of the higher-order zincate species. Subsequent investigation into diarylzinc as reagents in Negishi cross-coupling have shown they transmetalate directly without the use of halide additive in THF alone producing arylzinc halide as a resting state. Once the dielectric of the solvent becomes sufficiently polar, coupling resumes, and the aryl moiety transmetalates to palladium. The optimized protocol using Pd-PEPPSI-IPent allowed for the coupling of a variety of alkyl- and aryl- organozinc reagents providing the corresponding products in good to quantitative yields. Moreover, the developed protocol is generally applicable and tolerant of a variety of functional groups including esters, and nitriles. Part II: An improved and efficient method for the preparation of sterically demanding Pd PEPPSI-IPent, IPentCl, IHept, and IHeptCl pre-catalysts are presented and the results of optimization for the multi-gram synthesis of 2,6-disubstituted anilines is discussed.","abstract_html":"Part I: An efficient method for alkyl-alkyl Negishi cross-coupling reaction of unactivated primary alkyl halides with higher-order zincate species (synthesized from dialkylzinc and a non-coordinating halide salt in situ) using Pd-PEPPSI-IPent (Pyridine-Enhanced Pre-catalyst Preparation Stabilization and Initiation) pre-catalyst has been developed. The method requires no additive (such as LiX) or use of a polar co-solvent (such as THF/DMI) and reactions proceed in THF solvent alone. The transmetalating species in alkyl-alkyl Negishi cross-coupling has been identified and the catalytic cycle has been amended to include the formation of the higher-order zincate species. Subsequent investigation into diarylzinc as reagents in Negishi cross-coupling have shown they transmetalate directly without the use of halide additive in THF alone producing arylzinc halide as a resting state. Once the dielectric of the solvent becomes sufficiently polar, coupling resumes, and the aryl moiety transmetalates to palladium. The optimized protocol using Pd-PEPPSI-IPent allowed for the coupling of a variety of alkyl- and aryl- organozinc reagents providing the corresponding products in good to quantitative yields. Moreover, the developed protocol is generally applicable and tolerant of a variety of functional groups including esters, and nitriles. Part II: An improved and efficient method for the preparation of sterically demanding Pd PEPPSI-IPent, IPentCl, IHept, and IHeptCl pre-catalysts are presented and the results of optimization for the multi-gram synthesis of 2,6-disubstituted anilines is discussed.","abstract_has_math":false,"creators":["McCann, Lucas Charles"],"institution":null,"degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Organ, Michael George"],"committee_chairs":[],"committee_members":[],"year":2016,"date_issued":"2016-09-20","date_published":"2016-09-20","updated_at":"2026-07-24T06:34:00Z","subjects":["Inorganic chemistry"],"languages":["en"],"rights":["Author owns copyright, except where explicitly noted. Please contact the author directly with licensing requests."],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/10315/32194","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Organ, Michael George"]},{"key":"dc:creator","label":"Author","values":["McCann, Lucas Charles"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2016-09-20T16:41:59Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2016-09-20T16:41:59Z"]},{"key":"dc:date.issued","label":"Date","values":["2016-09-20"]},{"key":"dc:type","label":"Dc Type","values":["Electronic Thesis or Dissertation"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Inorganic chemistry"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["Author owns copyright, except where explicitly noted. Please contact the author directly with licensing requests."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://hdl.handle.net/10315/32194"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Part I: An efficient method for alkyl-alkyl Negishi cross-coupling reaction of unactivated primary alkyl halides with higher-order zincate species (synthesized from dialkylzinc and a non-coordinating halide salt in situ) using Pd-PEPPSI-IPent (Pyridine-Enhanced Pre-catalyst Preparation Stabilization and Initiation) pre-catalyst has been developed. The method requires no additive (such as LiX) or use of a polar co-solvent (such as THF/DMI) and reactions proceed in THF solvent alone. The transmetalating species in alkyl-alkyl Negishi cross-coupling has been identified and the catalytic cycle has been amended to include the formation of the higher-order zincate species. Subsequent investigation into diarylzinc as reagents in Negishi cross-coupling have shown they transmetalate directly without the use of halide additive in THF alone producing arylzinc halide as a resting state. Once the dielectric of the solvent becomes sufficiently polar, coupling resumes, and the aryl moiety transmetalates to palladium. The optimized protocol using Pd-PEPPSI-IPent allowed for the coupling of a variety of alkyl- and aryl- organozinc reagents providing the corresponding products in good to quantitative yields. Moreover, the developed protocol is generally applicable and tolerant of a variety of functional groups including esters, and nitriles. Part II: An improved and efficient method for the preparation of sterically demanding Pd PEPPSI-IPent, IPentCl, IHept, and IHeptCl pre-catalysts are presented and the results of optimization for the multi-gram synthesis of 2,6-disubstituted anilines is discussed."]},{"key":"dc:title","label":"Title","values":["Part I: Mechanistic Insight in Alkyl-Alkyl and Aryl-Aryl Negishi Cross-Coupling Part II: Large Scale Synthesis of NHC Precursors: 2,6-DI(3-Pentyl) Aniline and 2,6-DI (4-Heptyl) Aniline"]}]}],"canonical_facts":{"dc:contributor.advisor":["Organ, Michael George"],"dc:creator":["McCann, Lucas Charles"],"dc:date.accessioned":["2016-09-20T16:41:59Z"],"dc:date.available":["2016-09-20T16:41:59Z"],"dc:date.issued":["2016-09-20"],"dc:description.abstract":["Part I: An efficient method for alkyl-alkyl Negishi cross-coupling reaction of unactivated primary alkyl halides with higher-order zincate species (synthesized from dialkylzinc and a non-coordinating halide salt in situ) using Pd-PEPPSI-IPent (Pyridine-Enhanced Pre-catalyst Preparation Stabilization and Initiation) pre-catalyst has been developed. The method requires no additive (such as LiX) or use of a polar co-solvent (such as THF/DMI) and reactions proceed in THF solvent alone. The transmetalating species in alkyl-alkyl Negishi cross-coupling has been identified and the catalytic cycle has been amended to include the formation of the higher-order zincate species. Subsequent investigation into diarylzinc as reagents in Negishi cross-coupling have shown they transmetalate directly without the use of halide additive in THF alone producing arylzinc halide as a resting state. Once the dielectric of the solvent becomes sufficiently polar, coupling resumes, and the aryl moiety transmetalates to palladium. The optimized protocol using Pd-PEPPSI-IPent allowed for the coupling of a variety of alkyl- and aryl- organozinc reagents providing the corresponding products in good to quantitative yields. Moreover, the developed protocol is generally applicable and tolerant of a variety of functional groups including esters, and nitriles. Part II: An improved and efficient method for the preparation of sterically demanding Pd PEPPSI-IPent, IPentCl, IHept, and IHeptCl pre-catalysts are presented and the results of optimization for the multi-gram synthesis of 2,6-disubstituted anilines is discussed."],"dc:identifier.uri":["http://hdl.handle.net/10315/32194"],"dc:language.iso":["en"],"dc:rights":["Author owns copyright, except where explicitly noted. Please contact the author directly with licensing requests."],"dc:subject":["Inorganic chemistry"],"dc:title":["Part I: Mechanistic Insight in Alkyl-Alkyl and Aryl-Aryl Negishi Cross-Coupling Part II: Large Scale Synthesis of NHC Precursors: 2,6-DI(3-Pentyl) Aniline and 2,6-DI (4-Heptyl) Aniline"],"dc:type":["Electronic Thesis or Dissertation"]},"updated_at":"2026-07-24T06:34:00Z"}