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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
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.
Visa övriga samt affilieringar
2003 (Engelska)Ingår i: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 9, nr 14, s. 3445-3449Artikel i tidskrift (Refereegranskat) Published
Ort, förlag, år, upplaga, sidor
2003. Vol. 9, nr 14, s. 3445-3449
Identifikatorer
URN: urn:nbn:se:su:diva-22602OAI: oai:DiVA.org:su-22602DiVA, id: diva2:189145
Anmärkning
Part of urn:nbn:se:su:diva-100Tillgänglig från: 2004-04-07 Skapad: 2004-04-07 Senast uppdaterad: 2017-12-13Bibliografiskt granskad
Ingår i avhandling
1. Palladium-Catalyzed Carbocyclizations of Allenes with Unsaturated Hydrocarbons
Öppna denna publikation i ny flik eller fönster >>Palladium-Catalyzed Carbocyclizations of Allenes with Unsaturated Hydrocarbons
2004 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
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.

Ort, förlag, år, upplaga, sidor
Stockholm: Institutionen för organisk kemi, 2004. s. 53
Nyckelord
Palladium-catalysis, Allenes
Nationell ämneskategori
Organisk kemi
Identifikatorer
urn:nbn:se:su:diva-100 (URN)91-7265-863-0 (ISBN)
Disputation
2004-04-29, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 14:00
Opponent
Handledare
Tillgänglig från: 2004-04-07 Skapad: 2004-04-07Bibliografiskt granskad
2. Studies on Palladium-Catalyzed Carbocyclizations of Allene-Substituted Olefins and 1,3-Dienes
Öppna denna publikation i ny flik eller fönster >>Studies on Palladium-Catalyzed Carbocyclizations of Allene-Substituted Olefins and 1,3-Dienes
2006 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
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.

Ort, förlag, år, upplaga, sidor
Stockholm: Institutionen för organisk kemi, 2006. s. 66
Nyckelord
Organometallic Chemistry, Homogenous Catalysis, Palladium, Allenes, C-C bond formation
Nationell ämneskategori
Organisk kemi
Identifikatorer
urn:nbn:se:su:diva-794 (URN)91-7155-198-0 (ISBN)
Disputation
2006-02-02, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 14:00 (Engelska)
Opponent
Handledare
Tillgänglig från: 2006-01-12 Skapad: 2006-01-12 Senast uppdaterad: 2010-01-13Bibliografiskt granskad

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