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Palladium-Catalyzed Oxidative Carbocyclization/Arylation of Enallenes
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.
2011 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 13, no 21, 5838-5841 p.Article in journal (Refereed) Published
Abstract [en]

A stereoselective palladium-catalyzed oxidative carbocyclization/arylation of enallenes is described. The reaction shows wide tolerance toward highly functionalized arylboronic acids and results In a cis addition of two carbon moieties to an olefin in good to excellent yields.

Place, publisher, year, edition, pages
2011. Vol. 13, no 21, 5838-5841 p.
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-71716DOI: 10.1021/ol202451fISI: 000296212200034OAI: oai:DiVA.org:su-71716DiVA: diva2:485564
Funder
EU, European Research CouncilSwedish Research Council
Note

3

Available from: 2012-01-29 Created: 2012-01-29 Last updated: 2017-12-08Bibliographically approved
In thesis
1. Palladium(II)-Catalyzed Oxidative Cyclization Strategies: Selective Formation of New C-C and C-N Bonds
Open this publication in new window or tab >>Palladium(II)-Catalyzed Oxidative Cyclization Strategies: Selective Formation of New C-C and C-N Bonds
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The main focus of this thesis has been directed towards preparation and oxidative carbocyclization of en-, dien- and aza-enallenes.

In the first part of this thesis, a stereoselective oxidative carbocyclization of dienallenes was realized. By employing cheap and readily available palladium trifluoroacetate we were able to efficiently cyclize a variety of dienallenes into hydroxylated carbocycles in high yield and high selectivity. This oxidative process was compatible with two different reoxidation protocols: one relying on p-benzoquinone (BQ) as the oxidant and the other employing molecular oxygen as the oxidant.

In the second part of the thesis the carbocyclization methodology was extended to include carbocyclization of aza-enallenes. This was achieved in two distinct steps. First, a copper-catalyzed coupling of allylic sulfonamides with bromoallenes was developed, giving access to the corresponding aza-enallenes. Subjecting these substrates to catalytic amounts of palladium acetate, along with BQ as the oxidant, rendered N-heterocycles in good yield. The reactivity of these N-heterocycles towards activated dienophiles was later exploited in a tandem (aerobic) oxidative carbocyclization/Diels-Alder reaction.

The third topic involves efficient oxidative arylative/borylative carbocyclization of enallenes. These reactions, catalyzed by palladium acetate, relies on transmetallation of a (σ-alkyl)palladium(II) intermediate with diboranes or arylboronic acids. With this novel methodology we were able to obtain an array of arylated or borylated carbocycles, as single diastereomers, in high yield.

Finally, we developed a palladium(II)-catalyzed cyclization of allylic carbamates. This mild, operationally simple, and scalable catalytic reaction opens up access to an array of oxazolidinones in high yield and excellent diastereoselectivity.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2012. 88 p.
Keyword
Carbocyclization, Palladium Catalysis, Oxidation, Cyclization, Enallenes, Aza-Enallenes, Dienallenes, Allenylation, Oxazolidinones, Biomimetic, Arylation, Borylation, Transmetallation
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-75435 (URN)978-91-7447-495-4 (ISBN)
Public defence
2012-05-24, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 13:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 6: Manuscript.

Available from: 2012-05-02 Created: 2012-04-18 Last updated: 2013-01-03Bibliographically approved
2. Palladium(II)-Catalyzed Oxidative Carbocyclization: Stereoselective Formation of C–C and C–B Bonds
Open this publication in new window or tab >>Palladium(II)-Catalyzed Oxidative Carbocyclization: Stereoselective Formation of C–C and C–B Bonds
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Transition metal catalysis has emerged as one of the most versatile methods for the selective formation of carbon–carbon and carbon–heteroatom bonds. In particular, oxidative carbon–carbon bond forming reactions have been widely studied due to their atom economic feature. This thesis has been focused on the development of new palladium(II)-catalyzed carbocyclization reactions under oxidative conditions.

The first part of the thesis describes the palladium(II)-catalyzed oxidative carbocyclization-borylation and -arylation of enallenes. In these reactions, the (σ-alkyl)palladium(II) intermediate, which was shown previously to undergo β-hydride elimination, could be trapped in situ by organoboron reagents (B2pin2 and arylboronic acids) to form new carbon–boron and carbon–carbon bonds. Through these two protocols, a range of borylated and arylated carbocycles were obtained as single diastereomers in high yields.

The second part deals with a palladium(II)-catalyzed oxidative diarylative carbocyclization of enynes. The reaction was proposed to start with a syn-arylpalladation of an alkyne, followed by insertion of the coordinated alkene. Subsequent arylation afforded a series of valuable diarylated tetrahydrofuran and tetrahydropyran products.

The final part of the thesis advances the previously developed palladium(II)-catalyzed oxidative carbocyclization-borylation of enallenes in an enantioselective manner. C2-symmetric chiral phosphoric acids were used as the novel co-catalyst to trigger the enantioselective formation of intramolecular carbon–carbon bonds. By using this chiral anion strategy, a number of enallenes were converted to the borylated carbocycles with high to excellent enantioselectivity.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2014. 72 p.
Keyword
Carbocyclization, Palladium catalysis, Oxidation, Enallenes, Enynes, Borylation, Arylation, Asymmetric Catalysis, Chiral Brønsted acids, Chiral anion
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-108669 (URN)978-91-7649-020-4 (ISBN)
Public defence
2014-12-05, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 14:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 4: Manuscript.

Available from: 2014-11-13 Created: 2014-10-31 Last updated: 2017-03-16Bibliographically approved

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