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Palladium Pincer-Complex Catalyzed Trimethyltin Substitution of Functionalized Propargylic Substrates: An Efficient Route to Propargyl- and Allenyl-Stannanes
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2004 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 126, no 2, 474-476 p.Article in journal (Refereed) Published
Place, publisher, year, edition, pages
2004. Vol. 126, no 2, 474-476 p.
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-23631OAI: oai:DiVA.org:su-23631DiVA: diva2:193603
Note

Part of urn:nbn:se:su:diva-416

Available from: 2005-03-24 Created: 2005-03-24 Last updated: 2017-12-13Bibliographically approved
In thesis
1. Employment of Palladium Pincer Complex Catalysts and Lewis Acids for Synthesis and Transformation of Organometallic Compounds
Open this publication in new window or tab >>Employment of Palladium Pincer Complex Catalysts and Lewis Acids for Synthesis and Transformation of Organometallic Compounds
2005 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis is mainly focused on the development of new palladium catalyzed transformations using so-called “pincer” complexes. These complexes were applied as catalysts in two important areas of organometallic chemistry: substitution of propargylic substrates by dimetallic reagents; and allylation of aldehydes and imines by allylstannanes. In addition, this thesis includes studies on Lewis acid mediated cyclization reactions of allylsilanes with aldehydes.

Pincer complex catalyzed substitution of various propargylic substrates could be achieved under mild conditions using tin and silicon based dimetallic reagents to obtain propargyl- and allenylstannanes and silanes. The regioselectivity of the substitution reaction strongly depends on the steric and electronic effects of the propargylic substrate. According to our mechanistic studies the key intermediate of the reaction is an organostannane (or silane) coordinated pincer complex. DFT modeling studies on the transfer of the trimethylstannyl functionality to the propargylic substrate revealed a novel mechanism, which is based on the unique topology of the pincer-complex catalysts.

Our further studies showed that palladium pincer complexes can be employed as efficient catalysts for electrophilic allylic substitution of allylstannanes with aldehyde and imine substrates. In contrast to previous applications for electrophilic allylic substitutions via bis-allylpalladium complexes, this reaction involves mono-allylpalladium intermediates which were observed by 1H-NMR spectroscopy.

The last chapter of this thesis is focused on Lewis-acid mediated cyclization of hydroxy functionalized allylsilanes, which afford tetrahydropyran derivatives with a high stereoselectivity.

Place, publisher, year, edition, pages
Stockholm: Institutionen för organisk kemi, 2005. 58 p.
National Category
Chemical Sciences
Identifiers
urn:nbn:se:su:diva-416 (URN)91-7155-026-7 (ISBN)
Public defence
2005-04-29, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 10:00 (English)
Opponent
Supervisors
Available from: 2005-03-24 Created: 2005-03-24 Last updated: 2010-02-11Bibliographically approved

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