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Palladium-Catalyzed Oxidative Arylating Carbocyclization of Allenynes: Control of Selectivity and Role of H2O
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.
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2014 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 53, no 33, 8696-8699 p.Article in journal (Refereed) Published
Abstract [en]

Highly selective protocols for the carbocyclization/arylation of allenynes using arylboronic acids are reported. Arylated vinylallenes are obtained with the use of BF3 center dot Et2O as an additive, whereas addition of water leads to arylated trienes. These conditions provide the respective products with excellent selectivities (generally > 97:3) for a range of boronic acids and different allenynes. It has been revealed that water plays a crucial role for the product distribution.

Place, publisher, year, edition, pages
Weinheim: Wiley-VCH Verlag GmbH & Co. KGaA , 2014. Vol. 53, no 33, 8696-8699 p.
Keyword [en]
allenes, boronic acids, cyclization, oxidation, palladium
National Category
Chemical Sciences Organic Chemistry
URN: urn:nbn:se:su:diva-107580DOI: 10.1002/anie.201404264ISI: 000340523500025OAI: diva2:748656
Knut and Alice Wallenberg FoundationEU, European Research CouncilSwedish Research CouncilBerzelii Centre EXSELENTThe Wenner-Gren Foundation


Available from: 2014-09-21 Created: 2014-09-20 Last updated: 2016-04-11Bibliographically approved
In thesis
1. Palladium(II)-Catalyzed Oxidative Carbocyclization/Functionalization of Allenynes
Open this publication in new window or tab >>Palladium(II)-Catalyzed Oxidative Carbocyclization/Functionalization of Allenynes
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The selective formation of carbon-carbon bonds constitutes a key transformation in organic synthesis with useful applications in pharmaceutical or material industry. A particularly versatile tool for carbon-carbon as well as carbon-heteroatom bond formation is palladium catalysis, which allows for mild and selective routes even towards complex structures.

The work in this thesis describes the development and the mechanistic investigation of a palladium(II)-catalyzed oxidative carbocyclization/functionalization methodology, which converts 1,5-allenynes into either arylated or borylated carbocycles. To this end, either boronic acids or B2pin2 are employed and 1,4-benzoquinone serves as the stoichiometric oxidant. These protocols provide access to two products, a cyclic triene and a cyclic vinylallene. Their formation is dependent on the substrate structure as the latter product requires a propargylic C–H bond to be present in the substrate. Based on kinetic isotope effects, mechanisms involving either an initial allenic or propargylic C–H abstraction, respectively, were proposed. Full control of product selectivity to give either trienes or vinylallenes was achieved by modifying the reaction conditions with additives. Using substoichiometric amounts of BF3·OEt2 leads selectively to borylated or arylated vinylallenes. Under arylating conditions the reaction is zero order in allenyne and oxidant, and first order in phenylboronic acid. Transmetalation and, to some extent, propargylic C–H cleavage were found to be turnover-limiting. The selective reaction towards functionalized trienes was achieved by addition of either substoichiometric LiOAc·2H2O (borylation) or excess amounts of H2O (arylation). For the latter case, a kinetic study revealed an unusually slow catalyst activation. Lower concentrations of H2O gave product mixtures, and it was shown that vinylallenes are formed with either boronic acid or boroxine, whereas the formation of trienes requires boronic acid.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2014. 95 p.
palladium catalysis, oxidation, carbocyclization, allenynes, boron reagents, kinetics, selectivity, reaction mechanism
National Category
Organic Chemistry
Research subject
Organic Chemistry
urn:nbn:se:su:diva-108587 (URN)978-91-7649-019-8 (ISBN)
Public defence
2014-12-04, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 14:00 (English)

At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 3: Manuscript.

Available from: 2014-11-12 Created: 2014-10-30 Last updated: 2014-11-21Bibliographically approved

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