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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

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dc.contributor.advisorOrgan, Michael George
dc.creatorMcCann, Lucas Charles
dc.date.accessioned2016-09-20T16:41:59Z
dc.date.available2016-09-20T16:41:59Z
dc.date.copyright2015-10-30
dc.date.issued2016-09-20
dc.date.updated2016-09-20T16:41:59Z
dc.degree.disciplineChemistry
dc.degree.levelDoctoral
dc.degree.namePhD - Doctor of Philosophy
dc.description.abstractPart 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.urihttp://hdl.handle.net/10315/32194
dc.language.isoen
dc.rightsAuthor owns copyright, except where explicitly noted. Please contact the author directly with licensing requests.
dc.subjectInorganic chemistry
dc.subject.keywordsCross-coupling
dc.subject.keywordsPalladium
dc.subject.keywordsZincate
dc.subject.keywordsZinc
dc.subject.keywordsChemistry
dc.subject.keywordsOrganic chemistry
dc.subject.keywordsMethodology
dc.subject.keywordsIndustrial chemistry
dc.subject.keywordsPd-PEPPSI
dc.subject.keywordsPEPPSI
dc.subject.keywordsPEPPSI catalyst
dc.subject.keywordsSynthesis
dc.subject.keywordsOrganometallic chemistry
dc.subject.keywordsOrganometallic
dc.subject.keywordsInorganic
dc.subject.keywordsInorganic chemistry
dc.subject.keywordsScale-up
dc.subject.keywordsProcess chemistry
dc.subject.keywordsOptimization
dc.subject.keywordsNegishi
dc.subject.keywordsNegishi Cross-coupling
dc.subject.keywordsAlkyl-alkyl
dc.subject.keywordsBond formation
dc.subject.keywordsNHC
dc.subject.keywordsN-heterocyclic carbene
dc.subject.keywordsCarbene
dc.subject.keywordsMechanistic determination
dc.subject.keywordsReaction mechanism
dc.subject.keywordsAryl-aryl
dc.subject.keywordsPd-PEPPSI-IPent
dc.subject.keywordsPd-PEPPSI-IHept
dc.subject.keywordsPd-PEPPSI-IPr
dc.subject.keywordsPd-PEPPSI-IPentCl
dc.subject.keywordsPd-PEPPSI-IHeptCl
dc.subject.keywords2
dc.subject.keywords6-DI(4-HEPTYL)ANILINE
dc.subject.keywords6-DI(3-PENTYL)ANILINE
dc.subject.keywordsLarge-scale
dc.titlePart 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.typeElectronic Thesis or Dissertation

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