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An unexpectedly mild thermal alder-ene-type cyclization of enallenes
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Responsible organisation
2006 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, ISSN 0022-3263, Vol. 71, no 7, 2914-2917 p.Article in journal (Refereed) Published
Abstract [en]

A mild, thermal Alder-ene reaction of enallenes has been developed. The allenic double bond acts as the "ene" and generates a carbon-carbon bond to an unactivated olefinic "enophile" in DMF at 120 degrees C to give [n.3.0] bicyclic systems (n = 3-5) in good yields. Except for a minor [2 + 2] cycloaddition byproduct, the reaction proceeded with complete atom economy, as there is no requirement of a catalyst or additional reactants, and no waste products are formed in the process.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2006. Vol. 71, no 7, 2914-2917 p.
Keyword [en]
pd-catalyzed cycloisomerization, allenes, 1, 2-dialkylidenecycloalkanes, carbocyclization, alkylallene, alkenes
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:su:diva-25281DOI: 10.1021/jo060013gOAI: oai:DiVA.org:su-25281DiVA: diva2:199320
Note

Part of urn:nbn:se:su:diva-794

Available from: 2006-01-12 Created: 2006-01-12 Last updated: 2017-12-13Bibliographically approved
In thesis
1. 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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