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Direct Amide Coupling of Non-activated Carboxylic Acids and Amines Catalysed by Zirconium(IV) Chloride
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.
2012 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 18, no 13, 3822-3826 p.Article in journal (Refereed) Published
Place, publisher, year, edition, pages
2012. Vol. 18, no 13, 3822-3826 p.
Keyword [en]
amides, amines, carboxylic acids, homogeneous catalysis, zirconium
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-76257DOI: 10.1002/chem.201104055ISI: 000301775300002OAI: oai:DiVA.org:su-76257DiVA: diva2:528433
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Available from: 2012-05-25 Created: 2012-05-10 Last updated: 2017-12-07Bibliographically approved
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
2. Group (IV) Metal-Catalyzed Direct Amidation: Synthesis and Mechanistic Considerations
Open this publication in new window or tab >>Group (IV) Metal-Catalyzed Direct Amidation: Synthesis and Mechanistic Considerations
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The amide unit constitutes the backbone of proteins, and it is present in a large number of pharmaceutically active molecules, polymeric materials such as nylon and Kevlar, as well as in food additives like aspartame. Amides are produced in enormous amounts every year, thus, environmentally friendly and selective methods for their formation are of great importance. This thesis deals with the direct formation of amides from non-activated carboxylic acids and amines with the aid of group (IV) metal complexes. Water is the only by-product of this environmentally benign process. This fact stands in contrast to the most common methods for amide formation to date, which involve the use of waste-intensive, expensive and often toxic coupling reagents. The catalytic protocols presented herein use titanium, zirconium and hafnium complexes under mild reaction conditions to produce amides in good to excellent yields. Furthermore, carbamates are demonstrated to be suitable sources of gaseous amines for the formation of primary and tertiary amides under catalytic conditions. In addition, preliminary results from on-going mechanistic investigations of the zirconium- and hafnium-catalyzed processes are presented.

Abstract [sv]

Amidbindningen är en kemisk enhet som utgör ryggraden i proteiner, och som även återfinns i en stor mängd läkemedelsmolekyler, polymera material som nylon och Kevlar, samt i tillsatser i livsmedelsindustrin, exempelvis aspartam. Amider produceras i enorma mängder varje år, och det är av stor vikt att utveckla miljövänliga och selektiva metoder för deras framställning. Denna avhandling behandlar direkt amidering av icke-aktiverade karboxylsyror och aminer med hjälp av katalytiska mängder metallkomplex, baserade på titan, zirkonium och hafnium. Den enda biprodukten från denna amideringsreaktion är vatten. Jämfört med de metoder som generellt används idag för amidsyntes, så är de presenterade metoderna avsevärt mer miljövänliga med avseende på toxicitet hos reagensen såväl som på mängden avfall som genereras. Dessutom redovisas här en katalytisk metod för syntes av primära och tertiära amider genom att använda olika karbamat som källa till gasformiga aminer, vilka annars kan vara praktiskt svåra att arbeta med. Preliminära resultat från en pågående mekanistisk studie av de zirkonium- och hafnium-katalyserade processerna är också inkluderade.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2015. 77 p.
Keyword
catalysis, amide, carboxylic acid, amino acid, titanium, zirconium, hafnium
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-116955 (URN)978-91-7649-163-8 (ISBN)
Public defence
2015-06-12, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 13:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 2: Accepted.

Available from: 2015-05-21 Created: 2015-05-04 Last updated: 2015-06-24Bibliographically approved

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