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Palladium(II)-Catalyzed Oxidative Carbocyclization/Functionalization of Allenynes
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2013 (English)Licentiate thesis, comprehensive summary (Other academic)
Abstract [en]

Palladium catalysis has emerged as an outstanding tool in synthetic organic chemistry for the mild and selective formation of carbon-carbon and carbon-heteroatom bonds. This thesis has been directed towards the extension of palladium(II)-catalyzed carbocyclization chemistry under oxidative conditions. An oxidative carbocyclization/functionalization methodology utilizing boron-containing transmetalation reagents was exploited to convert 1,5-allenynes into either arylated or borylated carbocycles. Two protocols were developed that use minimal amounts of Pd(OAc)2, stoichiometric para-benzoquinone as the oxidant and either bis(pinacolato)diboron or different arylboronic acids under mild conditions. A wide substrate scope is applicable to both methods. When the allenyne substrate bears a propargylic hydrogen, two isomeric functionalized carbocycles can be formed. By controlling the reaction conditions the reaction can be directed towards either of these two isomeric products. Kinetic isotope effect studies suggest that the mechanism leading to the different products proceeds through allylic or propargylic C-H bond cleavage, respectively. Moreover, it was observed that water has an interesting effect on the product selectivity when arylboronic acids are used in the oxidative carbocyclization of allenynes.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University , 2013. , 59 p.
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-88935OAI: oai:DiVA.org:su-88935DiVA: diva2:614849
Presentation
2013-04-23, Magnéli Hall, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 11:00
Opponent
Supervisors
Available from: 2013-05-22 Created: 2013-04-08 Last updated: 2013-05-23Bibliographically approved
List of papers
1. Palladium-Catalyzed Oxidative Arylating Carbocyclization of Allenynes
Open this publication in new window or tab >>Palladium-Catalyzed Oxidative Arylating Carbocyclization of Allenynes
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2012 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 51, no 11, 2703-2707 p.Article in journal (Refereed) Published
Keyword
alkynes, allenes, cyclization, oxidation, palladium
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-78438 (URN)10.1002/anie.201107592 (DOI)000301173800031 ()
Funder
Swedish Research Council
Note

5

Available from: 2012-07-05 Created: 2012-07-04 Last updated: 2017-12-07Bibliographically approved
2. Control of Selectivity in Palladium-Catalyzed Oxidative Carbocyclization/Borylation of Allenynes
Open this publication in new window or tab >>Control of Selectivity in Palladium-Catalyzed Oxidative Carbocyclization/Borylation of Allenynes
2013 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 52, no 24, 6283-6287 p.Article in journal (Refereed) Published
Abstract [en]

In control: A highly selective carbocyclization/borylation of allenynes with bis(pinacolato)diboron (B2pin2) under palladium catalysis and with p-benzoquinone (BQ) as the oxidant was developed. The use of either LiOAc⋅2 H2O with 1,2-dichloroethane (DCE) as the solvent or BF3⋅Et2O together with THF is crucial for the selective formation of borylated trienes and vinylallenes, respectively.

Keyword
allenes, boronates, cyclization, oxidation, palladium
National Category
Chemical Sciences
Identifiers
urn:nbn:se:su:diva-90111 (URN)10.1002/anie.201301167 (DOI)000320375800028 ()
Funder
EU, European Research Council, 247014Swedish Research CouncilKnut and Alice Wallenberg FoundationThe Wenner-Gren FoundationBerzelii Centre EXSELENT
Note

AuthorCount: 3;

Available from: 2013-05-23 Created: 2013-05-23 Last updated: 2017-12-06Bibliographically approved
3. Investigation of Selectivity in Palladium-Catalyzed Oxidative Arylating Carbocyclization of Allenynes.
Open this publication in new window or tab >>Investigation of Selectivity in Palladium-Catalyzed Oxidative Arylating Carbocyclization of Allenynes.
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-90113 (URN)
Available from: 2013-05-23 Created: 2013-05-23 Last updated: 2013-05-23

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