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Dynamic Processes in the Copper-Catalyzed Substitution of Chiral Allylic Acetates Leading to Loss of Chiral Information
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Manuscript (Other academic)
URN: urn:nbn:se:su:diva-22682OAI: diva2:189260
Part of urn:nbn:se:su:diva-1031Available from: 2006-05-08 Created: 2006-05-08 Last updated: 2010-01-13Bibliographically approved
In thesis
1. Asymmetric Synthesis and Mechanistic Studies on Copper(I)-Catalyzed Substitution of Allylic Substrates
Open this publication in new window or tab >>Asymmetric Synthesis and Mechanistic Studies on Copper(I)-Catalyzed Substitution of Allylic Substrates
2006 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis deals with the copper-catalyzed substitution of allylic substrates.

In the first part of this thesis, the synthesis of a series of metallocenethiolates is described. The thiolates were examined as ligands in the enantioselective copper(I)-catalyzed γ-substitution of allylic acetates.

The second part describes a study on copper-catalyzed α-substitution of enantiomerically pure secondary allylic esters. It was observed that the degree of chirality transfer is strongly dependent on the reaction temperature. The loss of chiral information is consistent with an equilibration of the allylCu(III) intermediates prior to product formation, which is essential in order to realize a copper-catalyzed dynamic kinetic asymmetric transformation process.

The third part describes a study on copper-catalyzed stereoselective α-substitution of enantiopure acyclic allylic esters. This method, when combined, with ruthenium and enzyme catalyzed dynamic kinetic resolution of allylic alcohols, provides a straightforward route to pharmaceutically important α-methyl carboxylic acids.

The fourth part is a mechanistic study on the reaction of perfluoroallyl iodide with organocuprates. Experimental studies as well as theoretical calculations were used to explain the contrasting reactivity of perfluoroallyl iodide vs. allyl iodide in cuprate allylation reactions.

In the fifth part, the development of a practical and useful method for the preparation of pentasubstituted acylferrocenes is presented.

Place, publisher, year, edition, pages
Stockholm: Institutionen för organisk kemi, 2006. 53 p.
copper, allylic substitution, ferrocene, DYKAT, cross-coupling, homo-coupling, DFT
National Category
Organic Chemistry
urn:nbn:se:su:diva-1031 (URN)91-7155-280-4 (ISBN)
Public defence
2006-06-01, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 13:00
Available from: 2006-05-08 Created: 2006-05-08Bibliographically approved

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