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
Catalytic allylic C—H acetoxylation and benzoyloxylation via suggested (η3-allyl)palladium(IV) intermediates
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.
2009 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 11, no 23, 5518-5521 p.Article in journal (Refereed) Published
Abstract [en]

Palladium-catalyzed allylic acetoxylations and benzoyloxylations were carried out using iodonium salts. The reactions proceed under mild conditions with high regio- and stereoselectivity. The catalysis can be performed under both acidic and nonacidic conditions without use of BQ or other external oxidants and activator ligands. Deuterium labeling experiments clearly show that the catalytic reaction proceeds through (η3-allyl)palladium intermediates. A stoichiometric study with one of the catalysts provided evidence for the formation of a Pd(IV) species.

Place, publisher, year, edition, pages
American Chemical Society , 2009. Vol. 11, no 23, 5518-5521 p.
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-32430DOI: 10.1021/ol9023369ISI: 000272038200040OAI: oai:DiVA.org:su-32430DiVA: diva2:280522
Available from: 2009-12-10 Created: 2009-12-10 Last updated: 2010-05-21Bibliographically approved
In thesis
1. Catalytic Functionalization of Allylic Substrates by Palladium Pincer Complexes
Open this publication in new window or tab >>Catalytic Functionalization of Allylic Substrates by Palladium Pincer Complexes
2010 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis is based on the development of novel catalytic reactions for the synthesis and application of organometallic reagents. The main focus is directed towards organoboronate derivatives. We developed an efficient procedure for converting allylic alcohols to the corresponding allylboronates using palladium pincer complexes as catalysts. The reactions were performed under mild conditions with high selectivity, allowing further one-pot transformations. Using this approach, a variety of stereodefined homoallylic alcohols and amino acid derivatives were synthesized via trapping of the in situ generated allylboronate derivatives with an appropriate electrophile. The synthetic scope of these types of multi-component reactions is broad as many different substrate allylic alcohols may be used together with various electrophiles. Several aspects of these reactions were studied, including different reagents, catalysts and electrophiles.

Furthermore, we studied the possibility to use oxidizing reagents as an essential component in the functionalization of olefins. Two main strategies were utilized for these catalytic methods using palladium pincer complexes. The functional group was either transferred from the oxidizing reagent, or introduced via an oxidation-transmetallation route. We propose that both methods involve palladium(IV) intermediates thus expanding both the coordination sphere of palladium and the synthetic scope of pincer complex catalysis.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2010. 65 p.
Keyword
Catalysis, Palladium, Pincer Complex, Boron, Multicomponent Reaction
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-39065 (URN)978-91-7447-090-1 (ISBN)
Public defence
2010-06-22, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 13:00 (English)
Opponent
Supervisors
Note
At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 11: In press.Available from: 2010-05-24 Created: 2010-05-06 Last updated: 2010-05-21Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full text

Search in DiVA

By author/editor
Pilarski, Lukasz T.Selander, NicklasSzabó, Kálmán
By organisation
Department of Organic Chemistry
In the same journal
Organic Letters
Organic Chemistry

Search outside of DiVA

GoogleGoogle Scholar

doi
urn-nbn

Altmetric score

doi
urn-nbn
Total: 50 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