Fe-catalyzed cross-coupling of 1-substituted cyclopropyl tosylates & Rh(III) complexes in carbene transfer reactions: development of an azo metathesis

Tindall, Daniel James

Fe-catalyzed cross-coupling of 1-substituted cyclopropyl tosylates & Rh(III) complexes in carbene transfer reactions: development of an azo metathesis

dc.contributor.advisor	Fürstner, Alois
dc.contributor.author	Tindall, Daniel James
dc.contributor.referee	Krause, Norbert
dc.date.accepted	2018-06-22
dc.date.accessioned	2018-06-26T13:43:42Z
dc.date.available	2018-06-26T13:43:42Z
dc.date.issued	2018
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.identifier.uri	http://hdl.handle.net/2003/36939
dc.identifier.uri	http://dx.doi.org/10.17877/DE290R-18938
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.subject.rswk	Metathese	de
dc.subject.rswk	Katalyse	de
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.type.publicationtype	doctoralThesis	en
dcterms.accessRights	open access
eldorado.secondarypublication	false	de

Files

Original bundle

Now showing 1 - 1 of 1

Name:: Dissertation_Daniel James Tindall.pdf
Size:: 5.08 MB
Format:: Adobe Portable Document Format
Description:: DNB

Download

License bundle

Now showing 1 - 1 of 1

Name:: license.txt
Size:: 4.85 KB
Format:: Item-specific license agreed upon to submission
Description:

Download

Collections

Organische Chemie