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Catalytic reactions with palladium supported on mesocellular foam: Applications in hydrogenation, isomerization, and C-C bond forming reactions
Stockholm University, Faculty of Science, Department of Organic Chemistry. (Prof. Bäckvall group)
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The major part of this thesis concerns the development of catalytic methodologies based on palladium nanoparticles immobilized on aminopropyl-functionalized siliceous mesocellular foam (Pd0-AmP-MCF). The catalytic activity of the precursor to the nanocatalyst, PdII-AmP-MCF is also covered by this work.

In the first part the application of Pd0-AmP-MCF in Suzuki-Miyaura cross-coupling reactions and transfer hydrogenation of alkenes under microwave irradiation is described. Excellent reactivity was observed and a broad range of substrates were tolerated for both transformations. The Pd0-AmP-MCF exhibited high recyclability as well as low metal leaching in both cases.

The aim of the second part was to evaluate the catalytic efficiency of the closely related PdII-AmP-MCF for cycloisomerization of various acetylenic acids. The catalyst was able to promote formation of lactones under mild conditions using catalyst loadings of 0.3 - 0.5 mol% at temperatures of up to 50 oC in the presence of Et3N. By adding 1,4-benzoquinone to the reaction, the catalyst could be recycled four times without any observable decrease in the activity.

The selective arylation of indoles at the C-2 position using Pd-AmP-MCF and symmetric diaryliodonium salts is presented in the third part. These studies revealed that Pd0-AmP-MCF was more effective than PdII-AmP-MCF for this transformation. Variously substituted indoles as well as diaryliodonium salts were tolerated, giving arylated indoles in high yields within 15 h at 20 - 50 oC in H2O. Only very small amounts of Pd leaching were observed and in this case the catalyst exhibited moderate recyclability.

The final part of the thesis describes the selective hydrogenation of the C=C in different α,β-unsaturated systems. The double bond was efficiently hydrogenated in high yields both under batch and continuous-flow conditions. High recyclability and low metal leaching were observed in both cases.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University , 2015. , 83 p.
Keyword [en]
Mesocellular foam, Heterogeneous palladium catalysis, nanopalladium
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-122061ISBN: 978-91-7649-280-2 (print)OAI: oai:DiVA.org:su-122061DiVA: diva2:862434
Public defence
2015-12-11, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 4: Submitted. Paper 5: Submitted.

 

Available from: 2015-11-19 Created: 2015-10-22 Last updated: 2016-08-25Bibliographically approved
List of papers
1. Nanopalladium on Amino-Functionalized Mesocellular Foam: An Efficient Catalyst for Suzuki Reactions and Transfer Hydrogenations
Open this publication in new window or tab >>Nanopalladium on Amino-Functionalized Mesocellular Foam: An Efficient Catalyst for Suzuki Reactions and Transfer Hydrogenations
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2013 (English)In: ChemCatChem, ISSN 1867-3880, E-ISSN 1867-3899, Vol. 5, no 2, 612-618 p.Article in journal (Refereed) Published
Abstract [en]

The applications of a heterogeneous Pd0-AmP-MCF nanoparticle catalyst in Suzuki cross-coupling reactions and transfer hydrogenations of alkenes are described. The catalyst was highly efficient for both transformations, resulting in 1)coupling of a wide range of aryl halides with various boronic acids in high yields and 2)chemoselective reduction of a variety of alkenes with the use of 1-methyl-1,4-cyclohexadiene as hydrogen donor. Moreover, the catalyst can be recycled several times without any significant decrease in activity or leaching of metal into solution, making the protocol economical and environmentally friendly. In the case of the Suzuki cross-coupling, a 15-fold increase in reaction rate was observed if the reaction was performed under microwave irradiation compared to conventional heating in an oil bath.

Keyword
cross-coupling, heterogeneous catalysis, hydrogenation, nanoparticles, palladium
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-88678 (URN)10.1002/cctc.201200247 (DOI)000314239000029 ()
Funder
EU, European Research Council, 247014Knut and Alice Wallenberg Foundation
Note

AuthorCount:5;

Available from: 2013-03-26 Created: 2013-03-25 Last updated: 2017-12-06Bibliographically approved
2. Cycloisomerization of Acetylenic Acids to gamma-Alkylidene Lactones using a Palladium(II) Catalyst Supported on Amino-Functionalized Siliceous Mesocellular Foam
Open this publication in new window or tab >>Cycloisomerization of Acetylenic Acids to gamma-Alkylidene Lactones using a Palladium(II) Catalyst Supported on Amino-Functionalized Siliceous Mesocellular Foam
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2014 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 79, no 3, 1399-1405 p.Article in journal (Refereed) Published
Abstract [en]

Cycloisomerization of various gamma-acetylenic acids to their corresponding gamma-alkylidene lactones by the use of a heterogeneous Pd(II) catalyst supported on amino-functionalized siliceous mesocellular foam is described. Substrates containing terminal as well as internal alkynes were cyclized in high to excellent yields within 2-24 h under mild reaction conditions. The protocol exhibited high regio- and stereoselectivity, favoring the exo-dig product with high Z selectivity. Moreover, the catalyst displayed excellent stability under the employed reaction conditions, as demonstrated by its good recyclability and low leaching.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-102073 (URN)10.1021/jo4028006 (DOI)000331163800057 ()
Funder
Swedish Research CouncilBerzelii Centre EXSELENT
Note

AuthorCount:5;

Available from: 2014-03-28 Created: 2014-03-26 Last updated: 2017-12-05Bibliographically approved
3. C-2 Selective Arylation of Indoles with Heterogeneous Nanopalladium and Diaryliodonium Salts
Open this publication in new window or tab >>C-2 Selective Arylation of Indoles with Heterogeneous Nanopalladium and Diaryliodonium Salts
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2014 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 20, no 42, 13531-13535 p.Article in journal (Refereed) Published
Abstract [en]

A simple and efficient method to prepare synthetically useful 2-arylindoles is presented, using a heterogeneous Pd catalyst and diaryliodonium salts in water under mild conditions. A remarkably low leaching of metal catalyst was observed under the applied conditions. The developed protocol is highly C-2 selective and tolerates structural variations both in the indole and in the diaryliodonium salt. Arylations of both NH indoles and N-protected indoles with ortho-substituted, electron-rich, electron-deficient, or halogenated diaryliodonium salts were achieved to give the desired products in high to excellent isolated yields within 6 to 15 h at room temperature or 40 °C.

Place, publisher, year, edition, pages
Weinheim: , 2014
Keyword
arylation, hypervalent iodine, indoles, nanopalladium, palladium catalysis
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-107700 (URN)10.1002/chem.201404017 (DOI)000342797500013 ()
Funder
Berzelii Centre EXSELENTEU, European Research Council, ERC AdG 247014Swedish Research Council, 621- 2011-3608Swedish Research Council, 621-2013-4653
Available from: 2014-09-24 Created: 2014-09-24 Last updated: 2017-12-05Bibliographically approved
4. Mild and Selective Catalytic Hydrogenation of the C=C Bond in a,b-Unsaturated Carbonyl Compounds Using Supported Palladium Nanoparticles
Open this publication in new window or tab >>Mild and Selective Catalytic Hydrogenation of the C=C Bond in a,b-Unsaturated Carbonyl Compounds Using Supported Palladium Nanoparticles
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2016 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 22, no 21, 7184-7189 p.Article in journal (Refereed) Published
Abstract [en]

Chemoselective reduction of the C=C bond in a variety of α,β-unsaturated carbonyl compounds using supported palladium nanoparticles is reported. Three different heterogeneous catalysts were compared using 1 atm of H2: 1) nano-Pd on a metal–organic framework (MOF: Pd0-MIL-101-NH2(Cr)), 2) nano-Pd on a siliceous mesocellular foam (MCF: Pd0-AmP-MCF), and 3) commercially available palladium on carbon (Pd/C). Initial studies showed that the Pd@MOF and Pd@MCF nanocatalysts were superior in activity and selectivity compared to commercial Pd/C. Both Pd0-MIL-101-NH2(Cr) and Pd0-AmP-MCF were capable of delivering the desired products in very short reaction times (10–90 min) with low loadings of Pd (0.5–1 mol %). Additionally, the two catalytic systems exhibited high recyclability and very low levels of metal leaching.

Keyword
heterogeneous catalysis, mesocellular foam, metal–organic framework, palladium nanoparticles, selective hydrogenation
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-132708 (URN)10.1002/chem.201600878 (DOI)
Funder
Swedish Research CouncilVINNOVABerzelii Centre EXSELENTKnut and Alice Wallenberg Foundation
Available from: 2016-08-19 Created: 2016-08-19 Last updated: 2017-11-07Bibliographically approved
5. Nanopalladium-catalyzed Conjugate Reduction of Michael Acceptors – Application in Flow
Open this publication in new window or tab >>Nanopalladium-catalyzed Conjugate Reduction of Michael Acceptors – Application in Flow
(English)Article in journal (Refereed) Submitted
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-122060 (URN)
Available from: 2015-10-22 Created: 2015-10-22 Last updated: 2015-10-30Bibliographically approved

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