Alkylidene Dihydropyridines as Useful Intermediates for Functionalization of 4-Alkylpyridines

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dc.contributor.advisorOrellana, Arturo
dc.contributor.authorShi, Jiaqi
dc.date.accessioned2024-03-18T17:59:32Z
dc.date.available2024-03-18T17:59:32Z
dc.date.issued2024-03-16
dc.date.updated2024-03-16T10:48:49Z
dc.degree.disciplineChemistry
dc.degree.levelDoctoral
dc.degree.namePhD - Doctor of Philosophy
dc.description.abstractPyridines are widely used and extensively studied heterocyclic compounds in industry and academia. Developing mild and selective methods for functionalizing pyridines would facilitate the synthesis of more structurally diverse pyridine derivatives, which could aid the development of potential drug candidates and streamline the drug discovery process. Through a “soft-enolization” logic, 4-alkylpyridines can be readily converted to corresponding alkylidene dihydropyridines (ADHPs), enabling mild and selective palladium-catalyzed allylation and dehydrogenation, as previously shown by our group. During the mechanistic study of the allylation reaction, prompted by the low enantioselectivity of pyridine allylation using optically active ligands, our group demonstrated that ADHPs are “soft” nucleophiles towards the allylpalladium(II) complex. We thus began employing this class of intermediates as soft nucleophiles in other reactions. Here I will first discuss the work towards enantioselective allylation of 4-alkylpyridines. Then I will describe the conjugate addition of ADHPs to a,b-unsaturated ketones that are activated by triethylsilyl triflate. Finally, I will introduce the approach to unite piperidine and pyridine with a carbon atom through addition of ADHPs to protonated pyridines with subsequent transfer hydrogenation reaction.
dc.identifier.urihttps://hdl.handle.net/10315/41881
dc.languageen
dc.rightsAuthor owns copyright, except where explicitly noted. Please contact the author directly with licensing requests.
dc.subjectOrganic chemistry
dc.subject.keywordsAlkylidene dihydropyridine
dc.subject.keywordsADHP
dc.subject.keywordsPyridine
dc.subject.keywordsAlkylpyridine
dc.subject.keywordsAlkyl pyridine
dc.subject.keywordsPyridine functionalization
dc.subject.keywordsPiperidine
dc.subject.keywordsAllylation
dc.subject.keywordsPalladium catalysis
dc.subject.keywordsPyridylic allylation
dc.subject.keywordsDihydropyridine
dc.subject.keywordsDHP
dc.subject.keywordsLewis acid
dc.subject.keywordsUnsaturated ketone
dc.subject.keywordsConjugate addition
dc.subject.keywordsRegioselective conjugate addition
dc.subject.keywordsMichael addition
dc.subject.keywordsFunctional group tolerance
dc.subject.keywordsSoft nucleophile
dc.subject.keywordsHard nucleophile
dc.subject.keywordsPyridinium cation
dc.subject.keywordsPyridine activation
dc.subject.keywordsTriethysilyl triflate
dc.subject.keywordsEnantioselective allylation
dc.subject.keywordsLigand screen
dc.subject.keywords4-alkylpyridine
dc.subject.keywords4-pyridylic position
dc.subject.keywords4-pyridylic site
dc.subject.keywords4-pyridylic functionalization
dc.subject.keywordsPyridine hydrochloride
dc.subject.keywordsPyridinium chloride
dc.subject.keywordsTrans-dearomatization
dc.subject.keywordsTransfer hydrogenation
dc.titleAlkylidene Dihydropyridines as Useful Intermediates for Functionalization of 4-Alkylpyridines
dc.typeElectronic Thesis or Dissertation

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