Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.advisor | Fürstner, Alois | - |
dc.contributor.author | Tindall, Daniel James | - |
dc.date.accessioned | 2018-06-26T13:43:42Z | - |
dc.date.available | 2018-06-26T13:43:42Z | - |
dc.date.issued | 2018 | - |
dc.identifier.uri | http://hdl.handle.net/2003/36939 | - |
dc.identifier.uri | http://dx.doi.org/10.17877/DE290R-18938 | - |
dc.description.abstract | Firstly, 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.iso | en | de |
dc.subject | Katalyse | de |
dc.subject | Eisen | de |
dc.subject | Kreuzkupplung | de |
dc.subject | Rhodium | de |
dc.subject | Carbene | de |
dc.subject | Metathese | de |
dc.subject.ddc | 540 | - |
dc.title | Fe-catalyzed cross-coupling of 1-substituted cyclopropyl tosylates & Rh(III) complexes in carbene transfer reactions: development of an azo metathesis | en |
dc.type | Text | de |
dc.contributor.referee | Krause, Norbert | - |
dc.date.accepted | 2018-06-22 | - |
dc.type.publicationtype | doctoralThesis | en |
dc.subject.rswk | Metathese | de |
dc.subject.rswk | Katalyse | de |
dcterms.accessRights | open access | - |
eldorado.secondarypublication | false | de |
Appears in Collections: | Organische Chemie |
Files in This Item:
File | Description | Size | Format | |
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Dissertation_Daniel James Tindall.pdf | DNB | 5.2 MB | Adobe PDF | View/Open |
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