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Cycloisomerization of Acetylenic Acids to gamma-Alkylidene Lactones using a Palladium(II) Catalyst Supported on Amino-Functionalized Siliceous Mesocellular Foam
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.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
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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.

Place, publisher, year, edition, pages
2014. Vol. 79, no 3, 1399-1405 p.
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-102073DOI: 10.1021/jo4028006ISI: 000331163800057OAI: oai:DiVA.org:su-102073DiVA: diva2:708692
Funder
Swedish Research CouncilBerzelii Centre EXSELENT
Note

AuthorCount:5;

Available from: 2014-03-28 Created: 2014-03-26 Last updated: 2017-12-05Bibliographically 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. 83 p.
Keyword
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)
External cooperation:
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

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