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Allenes as Carbon Nucleophiles in Intramolecular Attack on (π-1,3-diene)Palladium Complexes: Evidence for trans-Carbopalladation of the 1,3-Diene
Stockholm University, Faculty of Science, Department of Organic Chemistry.
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2003 (English)In: Chemistry - A European Journal, ISSN 0947-6539, Vol. 9, no 14, 3445-3449 p.Article in journal (Refereed) Published
Place, publisher, year, edition, pages
2003. Vol. 9, no 14, 3445-3449 p.
Identifiers
URN: urn:nbn:se:su:diva-22602OAI: oai:DiVA.org:su-22602DiVA: diva2:189145
Note
Part of urn:nbn:se:su:diva-100Available from: 2004-04-07 Created: 2004-04-07 Last updated: 2010-01-13Bibliographically approved
In thesis
1. Palladium-Catalyzed Carbocyclizations of Allenes with Unsaturated Hydrocarbons
Open this publication in new window or tab >>Palladium-Catalyzed Carbocyclizations of Allenes with Unsaturated Hydrocarbons
2004 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Palladium-catalyzed reactions of unsaturated hydrocarbons are important processes in organic chemistry especially for the generation of ring systems. This thesis describes the development and mechanistic studies of carbocyclization reactions of allenes with olefins, allyls or 1,3-dienes catalyzed by palladium(0)- and palladium(II)-complexes. These reactions generally exhibit high stereo- and regioselectivity and give rise to stereodefined [n,3,0] bicyclic systems (n=3,4,5,6) in good to excellent yields. The mechanisms for these reactions were investigated with special attention directed to the intramolecular reaction of (π-allyl)palladium(II)-complexes and (π-1,3-diene)palladium(II)-complexes with allenes. It was demonstrated that the carbon-carbon bond formation occurred by nucleophilic attack of the middle carbon atom of the allene on the face of the allyl or 1,3-diene opposite to that of the palladium atom. Further, two new types of oxidative palladium(II)-catalyzed reactions between allenes and olefins or 1,3-dienes have been developed. These cyclizations constitute a new type of carbon-carbon bond forming reaction and there are support for a palladium(II)-catalyzed C-H activation at the allenic moiety rendering a vinylidienepalladium-intermediate followed by carbon-carbon bond formation via insertion of the olefin or 1,3-diene.

Place, publisher, year, edition, pages
Stockholm: Institutionen för organisk kemi, 2004. 53 p.
Keyword
Palladium-catalysis, Allenes
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-100 (URN)91-7265-863-0 (ISBN)
Public defence
2004-04-29, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 14:00
Opponent
Supervisors
Available from: 2004-04-07 Created: 2004-04-07Bibliographically approved
2. Studies on Palladium-Catalyzed Carbocyclizations of Allene-Substituted Olefins and 1,3-Dienes
Open this publication in new window or tab >>Studies on Palladium-Catalyzed Carbocyclizations of Allene-Substituted Olefins and 1,3-Dienes
2006 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis describes the development and mechanistic studies of carbocyclization reactions of allene-substituted olefins and 1,3-dienes, catalyzed by palladium(0) and palladium(II). These reactions results in the formation of [n,3,0] bicyclic systems (n = 3-5) with high stereoselectivity and in good to excellent yields.

The first carbocyclization presented is a novel palladium(0)-catalyzed cyclo- isomerization of allene-substituted olefins.

Secondly an efficient aerobic biomimetic system has been developed for a Pd(II)-catalyzed allylic oxidative carbocyclization of allene-substituted olefins.

Additionally, during the studies of palladium-catalyzed carbocyclizations of allene-substituted olefins, it was found that in the absence of palladium a mild thermal ene-reaction occurs. In this manner stereodefined, functionalized bicyclic compounds are obtained with good regioselectivity and in high yields.

The third and fourth carbocyclization developed are a palladium(II)-catalyzed oxidation and a palladium(0)-catalyzed intramolecular telomerization of allene-substituted 1,3-dienes.

A mechanistic study of the palladium(II)-catalyzed oxidation of allene-substituted 1,3-dienes was made, and reaction intermediates could be isolated. The stereochemistry of the reaction intermediates was assigned, and this made it possible to suggest a mechanism for the reaction. The presented mechanism is a trans carbopalladation of the 1,3-diene, where the allene act as the carbon nucleophile. Due to different stereochemical outcomes of the stoichiometric and catalytic reactions, this mechanism could only explain the stoichiometric reaction. Another mechanism for the catalytic reaction was suggested, which rationalizes both the regio- and stereochemistry of the products.

Place, publisher, year, edition, pages
Stockholm: Institutionen för organisk kemi, 2006. 66 p.
Keyword
Organometallic Chemistry, Homogenous Catalysis, Palladium, Allenes, C-C bond formation
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-794 (URN)91-7155-198-0 (ISBN)
Public defence
2006-02-02, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 14:00 (English)
Opponent
Supervisors
Available from: 2006-01-12 Created: 2006-01-12 Last updated: 2010-01-13Bibliographically approved

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