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Catalytic Formation of Amides
Stockholm University, Faculty of Science, Department of Organic Chemistry.
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: urn:nbn:se:su:diva-102129ISBN: 978-91-7447-897-6 (print)OAI: oai:DiVA.org:su-102129DiVA: diva2:708222
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
List of papers
1. Direct Amide Coupling of Non-activated Carboxylic Acids and Amines Catalysed by Zirconium(IV) Chloride
Open this publication in new window or tab >>Direct Amide Coupling of Non-activated Carboxylic Acids and Amines Catalysed by Zirconium(IV) Chloride
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
Keyword
amides, amines, carboxylic acids, homogeneous catalysis, zirconium
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-76257 (URN)10.1002/chem.201104055 (DOI)000301775300002 ()
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Available from: 2012-05-25 Created: 2012-05-10 Last updated: 2017-12-07Bibliographically approved
2. Titanium(IV) Isopropoxide as an Efficient Catalyst for Direct Amidation of Nonactivated Carboxylic Acids
Open this publication in new window or tab >>Titanium(IV) Isopropoxide as an Efficient Catalyst for Direct Amidation of Nonactivated Carboxylic Acids
2012 (English)In: Synlett: Accounts and Rapid Communications in Synthetic Organic Chemistry, ISSN 0936-5214, E-ISSN 1437-2096, Vol. 23, no 15, 2201-2204 p.Article in journal (Refereed) Published
Abstract [en]

Secondary and tertiary amides are formed in high yields, in an efficient and environmentally benign titanium(IV) isopropoxide catalyzed direct amidation of carboxylic acids with primary and secondary amines.

Keyword
amides, titanium, catalysis, carboxylic acids, amines
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-81823 (URN)10.1055/s-0032-1316993 (DOI)000308634800009 ()
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Note

AuthorCount:3;

Available from: 2012-11-07 Created: 2012-11-01 Last updated: 2017-12-07Bibliographically approved
3. 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
Open this publication in new window or tab >>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
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-102131 (URN)
Available from: 2014-03-27 Created: 2014-03-27 Last updated: 2014-03-28
4. Direct Catalytic Formation of Primary and Tertiary Amides from Non-Activated Carboxylic Acids, Employing Carbamates as Amine Source
Open this publication in new window or tab >>Direct Catalytic Formation of Primary and Tertiary Amides from Non-Activated Carboxylic Acids, Employing Carbamates as Amine Source
2012 (English)In: Advanced Synthesis and Catalysis, ISSN 1615-4150, E-ISSN 1615-4169, Vol. 354, no 13, 2531-2536 p.Article in journal (Refereed) Published
Abstract [en]

The operationally simple titanium(IV)- or zirconium(IV)-catalyzed direct amidation of non-activated carboxylic acids with ammonium carbamates generates primary, and tertiary N,N-dimethyl-substituted amides in good to excellent yields.

Keyword
amides, carboxylic acids, catalysis, titanium, zirconium
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-81253 (URN)10.1002/adsc.201200436 (DOI)000308329300025 ()
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Note

AuthorCount:3;

Available from: 2012-10-15 Created: 2012-10-15 Last updated: 2017-12-07Bibliographically approved
5. Efficient Palladium-Catalyzed Aminocarbonylation of Aryl Iodides Using Palladium Nanoparticles Dispersed on Siliceous Mesocellular Foam
Open this publication in new window or tab >>Efficient Palladium-Catalyzed Aminocarbonylation of Aryl Iodides Using Palladium Nanoparticles Dispersed on Siliceous Mesocellular Foam
Show others...
2014 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 20, no 20, 5885-5889 p.Article in journal (Refereed) Published
Abstract [en]

A highly dispersed nanopalladium catalyst supported on mesocellular foam (MCF), was successfully used in the heterogeneous catalysis of aminocarbonylation reactions. During the preliminary evaluation of this catalyst it was discovered that the supported palladium nanoparticles exhibited a “release and catch” effect, meaning that a minor amount of the heterogeneous palladium became soluble and catalyzed the reaction, after which it re-deposited onto the support.

Place, publisher, year, edition, pages
Weinheim: Wiley-VCH Verlag GmbH & Co. KGaA, 2014
Keyword
amides, aminocarbonylation, heterogeneous catalysis, palladium, release and catch
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-102132 (URN)10.1002/chem.201402029 (DOI)000335433500004 ()
Funder
EU, European Research Council, 247014Swedish Research CouncilKnut and Alice Wallenberg FoundationBerzelii Centre EXSELENT
Note

AuthorCount:6;

Available from: 2014-03-27 Created: 2014-03-27 Last updated: 2017-12-05Bibliographically approved

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