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.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.copyright | 2015-10-30 | |
dc.date.issued | 2016-09-20 | |
dc.date.updated | 2016-09-20T16:41:59Z | |
dc.degree.discipline | Chemistry | |
dc.degree.level | Doctoral | |
dc.degree.name | PhD - Doctor of Philosophy | |
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.subject.keywords | Cross-coupling | |
dc.subject.keywords | Palladium | |
dc.subject.keywords | Zincate | |
dc.subject.keywords | Zinc | |
dc.subject.keywords | Chemistry | |
dc.subject.keywords | Organic chemistry | |
dc.subject.keywords | Methodology | |
dc.subject.keywords | Industrial chemistry | |
dc.subject.keywords | Pd-PEPPSI | |
dc.subject.keywords | PEPPSI | |
dc.subject.keywords | PEPPSI catalyst | |
dc.subject.keywords | Synthesis | |
dc.subject.keywords | Organometallic chemistry | |
dc.subject.keywords | Organometallic | |
dc.subject.keywords | Inorganic | |
dc.subject.keywords | Inorganic chemistry | |
dc.subject.keywords | Scale-up | |
dc.subject.keywords | Process chemistry | |
dc.subject.keywords | Optimization | |
dc.subject.keywords | Negishi | |
dc.subject.keywords | Negishi Cross-coupling | |
dc.subject.keywords | Alkyl-alkyl | |
dc.subject.keywords | Bond formation | |
dc.subject.keywords | NHC | |
dc.subject.keywords | N-heterocyclic carbene | |
dc.subject.keywords | Carbene | |
dc.subject.keywords | Mechanistic determination | |
dc.subject.keywords | Reaction mechanism | |
dc.subject.keywords | Aryl-aryl | |
dc.subject.keywords | Pd-PEPPSI-IPent | |
dc.subject.keywords | Pd-PEPPSI-IHept | |
dc.subject.keywords | Pd-PEPPSI-IPr | |
dc.subject.keywords | Pd-PEPPSI-IPentCl | |
dc.subject.keywords | Pd-PEPPSI-IHeptCl | |
dc.subject.keywords | 2 | |
dc.subject.keywords | 6-DI(4-HEPTYL)ANILINE | |
dc.subject.keywords | 6-DI(3-PENTYL)ANILINE | |
dc.subject.keywords | Large-scale | |
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 |
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