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  Fe-Catalyzed Cross-Coupling of 1-Substituted Cyclopropyl Tosylates & Rh(III) Complexes in Carbene Transfer Reactions: Development of an Azo Metathesis

Tindall, D. J. (2018). Fe-Catalyzed Cross-Coupling of 1-Substituted Cyclopropyl Tosylates & Rh(III) Complexes in Carbene Transfer Reactions: Development of an Azo Metathesis. PhD Thesis, Technische Universität, Dortmund.

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 Creators:
Tindall, Daniel James1, Author              
Affiliations:
1Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445584              

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 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.

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Language(s): eng - English
 Dates: 2018-04-112018-06-222018-06-22
 Publication Status: Published in print
 Pages: 152
 Publishing info: Dortmund : Technische Universität
 Table of Contents: -
 Rev. Type: -
 Identifiers: DOI: 10.17877/DE290R-18938
 Degree: PhD

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