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dc.contributor.advisorFürstner, Alois-
dc.contributor.authorTindall, Daniel James-
dc.date.accessioned2018-06-26T13:43:42Z-
dc.date.available2018-06-26T13:43:42Z-
dc.date.issued2018-
dc.identifier.urihttp://hdl.handle.net/2003/36939-
dc.identifier.urihttp://dx.doi.org/10.17877/DE290R-18938-
dc.description.abstractFirstly, a novel Fe-catalyzed cross-coupling of 1-alkynylcyclopropyl tosylates and alkyl Grignard reagents was developed, which represents the first Fe-catalyzed cross-coupling of tert-alkyl electrophiles. The protocol allows regioselective access to the direct substitution products, in contrast to related Fe-catalyzed processes involving propargylic substrates which furnish exclusively the allene products. In addition, 1-vinyl¬cyclopropyl tosylates afforded the desired cross-coupling products when reacted with MeMgCl. If β-hydrogens were available on the nucleophile, mixtures of the cross-coupling product along with the reduced and the dimerized starting material were obtained. 1-Aryl- and 1-alkylcyclopropyl tosylates do not undergo this transformation which suggests that coordination of the substrate to the iron catalyst is necessary to allow for successful cross-coupling. Secondly, a Rh(III)-catalyzed metathesis of diazo compounds and azoarenes affording α-imino esters was developed. Key to the success and scalability of the reaction was irradiation of the reaction mixture with blue LEDs which facilitate the trans-to-cis isomerization of the azoarene and sets the scene for the metathesis to occur. This trans¬formation represents a new type of reaction of donor/acceptor carbenes and shows a broad scope with high yields and an appreciable compatibility with polar and apolar substituents giving rise to α-imino esters which could not easily be synthesized by traditional means.en
dc.language.isoende
dc.subjectKatalysede
dc.subjectEisende
dc.subjectKreuzkupplungde
dc.subjectRhodiumde
dc.subjectCarbenede
dc.subjectMetathesede
dc.subject.ddc540-
dc.titleFe-catalyzed cross-coupling of 1-substituted cyclopropyl tosylates & Rh(III) complexes in carbene transfer reactions: development of an azo metathesisen
dc.typeTextde
dc.contributor.refereeKrause, Norbert-
dc.date.accepted2018-06-22-
dc.type.publicationtypedoctoralThesisen
dc.subject.rswkMetathesede
dc.subject.rswkKatalysede
dcterms.accessRightsopen access-
eldorado.secondarypublicationfalsede
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