Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Control of the Regioselectivity in Catalytic Transformations Involving Amphiphilic Bis-allylpalladium Intermediates: Mechanism and Synthetic Applications
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.
2001 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 66, no 5, 1686-1693 p.Article in journal (Refereed) Published
Abstract [en]

Various dialkyl-substituted allyl chloride derivatives (2d−i) undergo regioselective palladium-catalyzed coupling reactions with allylstannanes (1a,b) and benzylidenemalonitrile (4), providing functionalized 1,7-octadienes in good yield. The catalytic reaction proceeds through an unsymmetrical amphiphilic bis-allylpalladium intermediate. An introductory electrophilic attack on the terminal position of the unsubstituted allyl moiety is followed by a nucleophilic attack on the alkyl-substituted allyl ligand. A theoretical analysis was performed by applying density functional theory at the B3PW91/DZ+P level to study the substituent effects on the electrophilic attack. According to the theoretical results, the high regioselectivity can be ascribed to the electronic effects of the alkyl substituents: The terminal alkyl groups destabilize the η13-bis-allylpalladium intermediate of the reaction; in addition, the alkyl substitution increases the activation barrier for the electrophilic attack.

Place, publisher, year, edition, pages
2001. Vol. 66, no 5, 1686-1693 p.
Identifiers
URN: urn:nbn:se:su:diva-22711DOI: 10.1021/jo001374dOAI: oai:DiVA.org:su-22711DiVA: diva2:189304
Note
Part of urn:nbn:se:su:diva-105Available from: 2004-04-22 Created: 2004-04-22 Last updated: 2017-12-13Bibliographically approved
In thesis
1. Development of Palladium-Catalyzed Transformations Involving η1-Allypalladium Species
Open this publication in new window or tab >>Development of Palladium-Catalyzed Transformations Involving η1-Allypalladium Species
2004 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis is focused on investigation of the structure, reactivity and isomerization reactions of η1-allylpalladium complexes, which are key intermediates in catalytic transformations. The first part of this thesis concerns the structure and reactivity of bis-allylpalladium complexes. We have studied the regioselective palladium-catalyzed coupling reaction of various dialkylsubstituted allyl chlorides with allylstannanes and benzylidenemalonitrile, affording functionalized 1,7-octadienes. We have also found that benzylidenemalonitrile can be replaced by isocyanates providing bis-allylated amides. The second part is a computational study on the η3-η1-η3 isomerization of allylpalladium complexes. The mechanism of the isomerization was studied by DFT. It was found that the isomerization involves tetra-coordinated η1-allylpalladium intermediates. Alkyl substitution of the metalated carbon leads to destabilization of the η1-allylpalladium intermediate, which increases the activation energy of the isomerization process. The last part describes our efforts to extend the synthetic scope of mono-allylpalladium chemistry to include catalytic allylation of imine and aldehyde substrates. We have found that this reactivity can be achieved by the use of strongly coordinating tridentate ligands on palladium. The η1-allylpalladium intermediate has been observed by NMR-spectroscopy, and DFT calculations have been performed to show the feasibility of an electrophilic attack occuring on the allyl moiety.

Place, publisher, year, edition, pages
Stockholm: Institutionen för organisk kemi, 2004. 65 p.
Keyword
Palladium, Homogenous catalysis, Allylation, Electrophilic substitution, Density functional calculations
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-105 (URN)91-7265-868-1 (ISBN)
Public defence
2004-05-14, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 10:00 (English)
Opponent
Supervisors
Available from: 2004-04-22 Created: 2004-04-22 Last updated: 2010-02-11Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full text

Search in DiVA

By author/editor
Szabó, Kálmán J.
By organisation
Department of Organic Chemistry
In the same journal
Journal of Organic Chemistry

Search outside of DiVA

GoogleGoogle Scholar

doi
urn-nbn

Altmetric score

doi
urn-nbn
Total: 23 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf