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Water as nucleophile in palladium-catalyzed oxidative carbohydroxylation of allene-substituted conjugated dienes
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.
2007 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 129, no 46, 14120-14121 p.Article in journal (Refereed) Published
Abstract [en]

An efficient palladium(II)-catalyzed oxidative carbohydroxylation of allene-substituted conjugated dienes in aqueous media has been developed. The reaction is conducted employing p-benzoquinone as the stoichiometric reoxidant for the palladium or under aerobic conditions with essentially the same outcome. It is worth mentioning that this is the first example of a palladium(II)-catalyzed oxidation where a carbon−carbon bond is formed in water and also one of the few cases of nucleophilic attack by water on a (π-allyl)palladium complex.

Place, publisher, year, edition, pages
2007. Vol. 129, no 46, 14120-14121 p.
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-11737DOI: 10.1021/ja075488jISI: 000251182000008OAI: oai:DiVA.org:su-11737DiVA: diva2:178256
Available from: 2008-01-14 Created: 2008-01-14 Last updated: 2017-12-13Bibliographically 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

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