New palladium-catalyzed approaches to heterocycles and carbocycles

dc.contributor.advisor Richard C. Larock
dc.contributor.author Dai, Guangxiu
dc.contributor.department Chemistry
dc.date 2018-08-24T23:06:52.000
dc.date.accessioned 2020-07-02T05:50:01Z
dc.date.available 2020-07-02T05:50:01Z
dc.date.copyright Wed Jan 01 00:00:00 UTC 2003
dc.date.issued 2003-01-01
dc.description.abstract <p>A wide variety of 3,4-disubstituted isoquinolines containing an aryl, allylic, benzylic, alkynyl and vinylic group at the 4 position have been prepared via cross-coupling of 2-(1-alkynyl)benzaldimines with organic halides in the presence of a palladium catalyst. The best results are obtained by employing 5 mol% Pd(PPh3)4, 5 equiv of K2CO 3 in DMF at 100°C. The electronic effect of the imine substrates and organic halides on the yields has been discussed.;3-Substituted 4-aroylisoquinolines have been prepared in high yields via carbonylative cross-coupling of 2-(1-alkynyl)benzaldimines with aromatic iodides or aroyl chlorides in the presence of a palladium catalyst under 1 atm of CO pressure. Imine substrates having an aryl, vinylic or alkyl substituent on the distal end of the triple bond all undergo this palladium-catalyzed carbonylative cross-coupling cyclization in high yields.;The palladium(II)-catalyzed oxidative carbonylation of 2-(1-alkynyl)benzaldimines for synthesis of the corresponding isoquinoline-4-carboxylates has been studied and the optimal reaction conditions have been investigated. Although this methodology study has not provided an efficient route to synthesize methyl 3-substituted isoquinoline-4-carboxylates in synthetically useful yields, it provides an insight into the nature of the palladium-catalyzed cyclization reactions promoted by organopalladium intermediates.;A novel intramolecular alkyl-to-aryl palladium rearrangement has been observed by trapping the arylpalladium intermediate with an olefin by a Heck reaction. The reaction conditions have been optimized and the reaction scope has been extensively studied. In all of the successful examples, migration products were isolated exclusively. In addition, this alkyl-to-aryl palladium migration can be controlled by simply modifying the reaction conditions.</p>
dc.format.mimetype application/pdf
dc.identifier archive/lib.dr.iastate.edu/rtd/573/
dc.identifier.articleid 1572
dc.identifier.contextkey 6075514
dc.identifier.doi https://doi.org/10.31274/rtd-180813-6
dc.identifier.s3bucket isulib-bepress-aws-west
dc.identifier.submissionpath rtd/573
dc.identifier.uri https://dr.lib.iastate.edu/handle/20.500.12876/78418
dc.language.iso en
dc.source.bitstream archive/lib.dr.iastate.edu/rtd/573/r_3085898.pdf|||Sat Jan 15 00:59:39 UTC 2022
dc.subject.disciplines Organic Chemistry
dc.subject.keywords Chemistry
dc.subject.keywords Organic chemistry
dc.title New palladium-catalyzed approaches to heterocycles and carbocycles
dc.type article
dc.type.genre dissertation
dspace.entity.type Publication
relation.isOrgUnitOfPublication 42864f6e-7a3d-4be3-8b5a-0ae3c3830a11
thesis.degree.level dissertation
thesis.degree.name Doctor of Philosophy
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