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Palladium(II)-Catalyzed Oxidative Cyclization Strategies: Selective Formation of New C-C and C-N Bonds
Stockholm University, Faculty of Science, Department of Organic Chemistry. (Jan-Erling Bäckvall)
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 [en]
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: urn:nbn:se:su:diva-75435ISBN: 978-91-7447-495-4 (print)OAI: oai:DiVA.org:su-75435DiVA: diva2:516638
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
List of papers
1. Water as nucleophile in palladium-catalyzed oxidative carbohydroxylation of allene-substituted conjugated dienes
Open this publication in new window or tab >>Water as nucleophile in palladium-catalyzed oxidative carbohydroxylation of allene-substituted conjugated dienes
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.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-11737 (URN)10.1021/ja075488j (DOI)000251182000008 ()
Available from: 2008-01-14 Created: 2008-01-14 Last updated: 2017-12-13Bibliographically approved
2. Copper-catalyzed N-allenylation of allylic sulfonamides
Open this publication in new window or tab >>Copper-catalyzed N-allenylation of allylic sulfonamides
2009 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 11, no 17, 3814-3817 p.Article in journal (Refereed) Published
Abstract [en]

Allylic allenic amides have been synthesized via a copper-catalyzed cross-coupling between allylic sulfonamides and bromoallenes in moderate to good yields. Copper(I) thiophene-2-carboxylate (CuTC) was used a source of copper with DMEDA as the ligand. The allenylated products obtained are potential substrates for palladium-catalyzed carbocyclizations.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-30453 (URN)10.1021/ol901294j (DOI)000269252900007 ()
Available from: 2009-10-14 Created: 2009-10-14 Last updated: 2017-12-12Bibliographically approved
3. Palladium(II)-catalyzed oxidative carbocyclization of aza-enallenes
Open this publication in new window or tab >>Palladium(II)-catalyzed oxidative carbocyclization of aza-enallenes
2010 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 49, no 27, 4624-4627 p.Article in journal (Refereed) Published
Abstract [en]

Live and let diene: A palladium(II)-catalyzed oxidative carbocyclization reaction of aza-enallenes provides access to potentially valuable heterocyclic dienes. In the presence of a dieneophile during the carbocyclization step, the products can react further in a one-pot cyclization/Diels–Alder sequence to give polycyclic products. BQ=para-benzoquinone

Keyword
allenes, carbocyclization, heterocycles, oxidation, palladium
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-45862 (URN)10.1002/anie.201000726 (DOI)
Available from: 2010-11-15 Created: 2010-11-15 Last updated: 2017-12-12Bibliographically approved
4. Palladium-Catalyzed Oxidative Borylative Carbocyclization of Enallenes
Open this publication in new window or tab >>Palladium-Catalyzed Oxidative Borylative Carbocyclization of Enallenes
2011 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 50, no 27, 6155-6159 p.Article in journal (Refereed) Published
Abstract [en]

An efficient oxidative carbocyclization/borylation of enallenes uses Pd(OAc)2 as the catalyst, B2pin2 as the boron-transfer reagent, and 1,4-benzoquinone (BQ) as the oxidant (see scheme). The reaction seems to take place through activation of the allene by a PdII complex to give an alkenyl–PdII intermediate followed by carbopalladation of the olefin and subsequent cleavage of the intermediate palladium–carbon bond by the boron reagent.

Keyword
borylation, carbocyclization, enallenes, oxidation, palladium
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-59546 (URN)10.1002/anie.201008032 (DOI)000292641200030 ()
Funder
EU, European Research CouncilSwedish Research CouncilKnut and Alice Wallenberg Foundation
Available from: 2011-07-05 Created: 2011-07-05 Last updated: 2017-12-11Bibliographically approved
5. Palladium-Catalyzed Oxidative Carbocyclization/Arylation of Enallenes
Open this publication in new window or tab >>Palladium-Catalyzed Oxidative Carbocyclization/Arylation of Enallenes
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.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-71716 (URN)10.1021/ol202451f (DOI)000296212200034 ()
Funder
EU, European Research CouncilSwedish Research Council
Note

3

Available from: 2012-01-29 Created: 2012-01-29 Last updated: 2017-12-08Bibliographically approved
6. Palladium(II)-Catalyzed Oxidative Cyclization of Allylic Tosylcarbamates: Scope, Derivatization, and Mechanistic Aspects
Open this publication in new window or tab >>Palladium(II)-Catalyzed Oxidative Cyclization of Allylic Tosylcarbamates: Scope, Derivatization, and Mechanistic Aspects
Show others...
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.

Keyword
amidopalladation, cyclization, oxazolidinones, oxidation, palladium
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-84775 (URN)10.1002/chem.201202359 (DOI)000311111900034 ()
Funder
Swedish Research Council
Note

AuthorCount:5;

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

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