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
Direct Boronation of Allyl Alcohols with Diboronic Acid Using Palladium Pincer-Complex Catalysis. A Remarkably Facile Allylic Displacement of the Hydroxy Group under Mild Reaction Conditions
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.
2006 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 128, no 14, 4588-4589 p.Article in journal (Refereed) Published
Abstract [en]

Allyl alcohols were converted to allyl boronic acids and subsequently to trifluoro(allyl)borates with tetrahydroxy diboron using palladium pincer-complex catalysis. These reactions are regio- and stereoselective proceeding with high isolated yields. Competitive boronation experiments indicate that under the applied reaction conditions the allylic displacement of a hydroxy group is faster than the displacement of an acetate leaving group. It is assumed that the hydroxy group of the allyl alcohol is converted to a diboronic acid ester functionality, which can easily be substituted.

Place, publisher, year, edition, pages
2006. Vol. 128, no 14, 4588-4589 p.
National Category
Other Basic Medicine
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-27749DOI: 10.1021/ja060468nOAI: oai:DiVA.org:su-27749DiVA: diva2:217725
Available from: 2009-05-15 Created: 2009-05-15 Last updated: 2010-05-21Bibliographically approved
In thesis
1. Development of New Synthetic Routes to Organoboronates by Catalytic Allylic Substitution and C-H bond Functionalization
Open this publication in new window or tab >>Development of New Synthetic Routes to Organoboronates by Catalytic Allylic Substitution and C-H bond Functionalization
2009 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis describes the development of new catalytic methods for the synthesis and application of organometallic reagents, mainly focusing on allylboronic acid derivatives. Thus, palladium pincer-complex catalysis has been applied for extending the scope of palladiumcatalyzed borylation reactions in the synthesis of regio- and stereodefined functionalized allylboronic acid derivatives. These novel allylboronic acids were also employed as substrates in palladium catalyzed regioselective coupling reactions with iodobenzenes. We have also developed a new one-pot sequence based on preparation of allyl- and vinylboronates

via catalytic carbon-hydrogen bond activation/borylation reactions. The synthetic scope of the reaction as well as mechanistic studies on the borylation process are presented. Finally, the synthesis of new chiral palladium pincer-complexes is described. These species were employed as catalysts in asymmetric electrophilic allyation of imines.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2009. 54 p.
Keyword
Palladium, Iridium, Boron, Catalysis
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-27753 (URN)978-91-7155-899-2 (ISBN)
Public defence
2009-06-11, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 13:00 (English)
Opponent
Supervisors
Available from: 2009-05-20 Created: 2009-05-15 Last updated: 2009-05-19Bibliographically approved
2. 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
Olsson, VilhelmSelander, NicklasSzabó, Kálmán
By organisation
Department of Organic Chemistry
In the same journal
Journal of the American Chemical Society
Other Basic Medicine

Search outside of DiVA

GoogleGoogle Scholar

doi
urn-nbn

Altmetric score

doi
urn-nbn
Total: 144 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