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Nanopalladium-catalyzed conjugate reduction of Michael acceptors - application in flow
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
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2016 (English)In: Green Chemistry, ISSN 1463-9262, E-ISSN 1463-9270, Vol. 18, no 9, p. 2632-2637Article in journal (Refereed) Published
Abstract [en]

A continuous-flow approach towards the selective nanopalladium-catalyzed hydrogenation of the olefinic bond in various Michael acceptors, which could lead to a greener and more sustainable process, has been developed. The nanopalladium is supported on aminofunctionalized mesocellular foam. Both aromatic and aliphatic substrates, covering a variation of functional groups such as acids, aldehydes, esters, ketones, and nitriles were selectively hydrogenated in high to excellent yields using two different flow-devices (H-Cube (R) and Vapourtec). The catalyst was able to hydrogenate cinnamaldehyde continuously for 24 h (in total hydrogenating 19 g cinnanmaldehyde using 70 mg of catalyst in the H-cube (R)) without showing any significant decrease in activity or selectivity. Furthermore, the metal leaching of the catalyst was found to be very low (ppb amounts) in the two flow devices.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2016. Vol. 18, no 9, p. 2632-2637
National Category
Chemical Sciences
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-131568DOI: 10.1039/c5gc02920aISI: 000375291100009OAI: oai:DiVA.org:su-131568DiVA, id: diva2:943095
Funder
Berzelii Centre EXSELENTSwedish Research CouncilVINNOVAKnut and Alice Wallenberg FoundationAvailable from: 2016-06-27 Created: 2016-06-21 Last updated: 2018-11-08Bibliographically approved
In thesis
1. Catalytic reactions with palladium supported on mesocellular foam: Applications in hydrogenation, isomerization, and C-C bond forming reactions
Open this publication in new window or tab >>Catalytic reactions with palladium supported on mesocellular foam: Applications in hydrogenation, isomerization, and C-C bond forming reactions
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. p. 83
Keywords
Mesocellular foam, Heterogeneous palladium catalysis, nanopalladium
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-122061 (URN)978-91-7649-280-2 (ISBN)
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: 2018-11-07Bibliographically approved

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Nagendiran, AnujaTai, Cheuk-WaiBäckvall, Jan-E.
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