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Studies on Palladiu...
Studies on Palladium-Catalyzed Carbocyclizations of Allene-Substituted Olefins and 1,3-Dienes
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- Närhi, Katja, 1976- (författare)
- Stockholms universitet,Institutionen för organisk kemi
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- Bäckvall, Jan-Erling (preses)
- Stockholms universitet,Institutionen för organisk kemi
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- Poli, Giovanni (opponent)
- Loboratorie de Chimie Organique, Université Pierre et Marie Curie, Paris VI
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(creator_code:org_t)
- ISBN 9171551980
- Stockholm : Institutionen för organisk kemi, 2006
- Engelska 66 s.
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Abstract
Ämnesord
Stäng
- 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.
Ämnesord
- NATURVETENSKAP -- Kemi -- Organisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Organic Chemistry (hsv//eng)
Nyckelord
- Organometallic Chemistry
- Homogenous Catalysis
- Palladium
- Allenes
- C-C bond formation
- Organic chemistry
- Organisk kemi
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