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Employment of Palladium Pincer Complex Catalysts and Lewis Acids for Synthesis and Transformation of Organometallic Compounds
Stockholm University, Faculty of Science, Department of Organic Chemistry.
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: urn:nbn:se:su:diva-416ISBN: 91-7155-026-7 (print)OAI: oai:DiVA.org:su-416DiVA: diva2:193608
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
List of papers
1. Palladium Pincer-Complex Catalyzed Trimethyltin Substitution of Functionalized Propargylic Substrates: An Efficient Route to Propargyl- and Allenyl-Stannanes
Open this publication in new window or tab >>Palladium Pincer-Complex Catalyzed Trimethyltin Substitution of Functionalized Propargylic Substrates: An Efficient Route to Propargyl- and Allenyl-Stannanes
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
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-23631 (URN)
Note

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

Available from: 2005-03-24 Created: 2005-03-24 Last updated: 2017-12-13Bibliographically approved
2. Palladium pincer complex-catalyzed stannyl and silyl transfer to propargylic substrates: Synthetic scope and mechanism
Open this publication in new window or tab >>Palladium pincer complex-catalyzed stannyl and silyl transfer to propargylic substrates: Synthetic scope and mechanism
2005 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 127, no 6, 1787-1796 p.Article in journal (Refereed) Published
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-23632 (URN)
Note

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

Available from: 2005-03-24 Created: 2005-03-24 Last updated: 2017-12-13Bibliographically approved
3. Palladium-Catalyzed Electrophilic Substitution via Monoallylpalladium Intermediates
Open this publication in new window or tab >>Palladium-Catalyzed Electrophilic Substitution via Monoallylpalladium Intermediates
2003 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 42, no 31, 3656-3658 p.Article in journal (Refereed) Published
Keyword
aldehydes, allylation, electrophilic substitution, homogenous catalysis, palladium
Identifiers
urn:nbn:se:su:diva-22714 (URN)10.1002/anie.200351477 (DOI)
Note
Part of urn:nbn:se:su:diva-105Available from: 2004-04-22 Created: 2004-04-22 Last updated: 2017-12-13Bibliographically approved
4. Pincer complex catalyzed allylation of aldehyde and imine substrates via nucleophilic η1-allyl palladium intermediates: A new concept for palladium catalyzed allylic substitution reactions
Open this publication in new window or tab >>Pincer complex catalyzed allylation of aldehyde and imine substrates via nucleophilic η1-allyl palladium intermediates: A new concept for palladium catalyzed allylic substitution reactions
2004 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 126, no 22, 7026-7033 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23634 (URN)10.1021/ja049357j (DOI)
Note
Part of urn:nbn:se:su:diva-416Available from: 2005-03-24 Created: 2005-03-24 Last updated: 2017-12-13Bibliographically approved
5. Synthesis of stereodefined vinyl-tetrahydropyran and vinyl-octahydrochromene derivatives via acetalization-cyclization of allylsilanes with aldehydes: Origin of the high stereoselectivity
Open this publication in new window or tab >>Synthesis of stereodefined vinyl-tetrahydropyran and vinyl-octahydrochromene derivatives via acetalization-cyclization of allylsilanes with aldehydes: Origin of the high stereoselectivity
2002 (English)In: Tetrahedron Letters, ISSN 0040-4039, E-ISSN 1359-8562, Vol. 43, no 6, 1123-1126 p.Article in journal (Refereed) Published
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-23635 (URN)
Note

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

Available from: 2005-03-24 Created: 2005-03-24 Last updated: 2017-12-13Bibliographically approved

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