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Palladium(II)-Catalyzed Oxidative Cyclization of Allylic Tosylcarbamates: Scope, Derivatization, and Mechanistic Aspects
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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2012 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 18, no 47, 15151-15157 p.Article, review/survey (Refereed) Published
Abstract [en]

A highly selective oxidative palladium(II)-catalyzed (Wacker-type) cyclization of readily available allylic tosylcarbamates is reported. This operationally simple catalytic reaction furnishes tosyl-protected vinyl-oxazolidinones, common precursors to syn-1,2-amino alcohols, in high yield and excellent diasteroselectivity (>20:1). It is demonstrated that both stoichiometric amounts of benzoquinone (BQ) as well as aerobic reoxidation (molecular oxygen) is suitable for this transformation. The title reaction is shown to proceed through overall trans-amidopalladation of the olefin followed by beta-hydride elimination. This process is scalable and the products are suitable for a range of subsequent transformations such as: kinetic resolution (KR) and oxidative Heck-, Wacker-, and metathesis reactions.

Place, publisher, year, edition, pages
2012. Vol. 18, no 47, 15151-15157 p.
Keyword [en]
amidopalladation, cyclization, oxazolidinones, oxidation, palladium
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-84775DOI: 10.1002/chem.201202359ISI: 000311111900034OAI: oai:DiVA.org:su-84775DiVA: diva2:582020
Funder
Swedish Research Council
Note

AuthorCount:5;

Available from: 2013-01-03 Created: 2013-01-02 Last updated: 2017-12-06Bibliographically 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)
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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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