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Zirconium(IV) Chloride Catalyzed Amide Formation from Carboxylic Acids and Amines: N-Benzyl-2-(phenylthio)acetamide and (S)-tert-butyl-2-(benzylcarbamoyl)pyrrolidine-1-carboxylate
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-102131OAI: oai:DiVA.org:su-102131DiVA: diva2:708218
Available from: 2014-03-27 Created: 2014-03-27 Last updated: 2014-03-28
In thesis
1. Catalytic Formation of Amides
Open this publication in new window or tab >>Catalytic Formation of Amides
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The amide functionality is a highly important chemical bond, found in a great number of synthetic products such as pharmaceuticals, polymers and agrochemicals. The focus of this thesis has been directed towards efficient, mild and environmentally friendly methods for amide formations. The first part is devoted to the investigation of a Lewis acid catalyzed protocol for direct condensation of non-activated carboxylic acids and amines. ZrCl4 was found to be a highly active catalyst and a low catalytic loading enabled for high yields of secondary and tertiary amides under relatively mild conditions. The second part of the thesis describes our investigations towards a catalytic method for primary amides. We demonstrated that the transformation was feasible by performing minor alterations to the previous Lewis acid based procedure. A variety of primary amides could be obtained in high yields by the use of carbamates, as a non-gaseous source of ammonia in combination with carboxylic acids and catalytic amounts of TiCl4 or ZrCl4. Furthermore, the protocol was extended to include catalytic formation of N,N-dimethylamides from non-activated carboxylic acids.

The use of immobilized metal nanoparticles as heterogeneous catalysts has emerged as a highly investigated research area. The final chapter of this thesis deals with the successful application of an immobilized Pd nanocatalyst for amide formation via the aminocarbonylation reaction of aryl iodides. The Pd0-AmP-MCF catalyst was found to operate through a “release and catch” mechanism, in which PdII species were released into the solution and then re-deposited onto the support after completion of the reaction. It was discovered that the combination of aryl halide and amine was the cause of the leaching, and furthermore that the homogeneous Pd species catalyzed the aminocarbonylation reaction. A selection of aryl iodides were evaluated using 2 mol% of Pd0-AmP-MCF under atmospheric pressure of CO, and the corresponding amides were obtained in good to high yields.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2014. 77 p.
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-102129 (URN)978-91-7447-897-6 (ISBN)
Public defence
2014-05-09, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 C, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 3: Manuscript.

Available from: 2014-04-14 Created: 2014-03-27 Last updated: 2014-04-14Bibliographically approved

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