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Palladium(II)-Catalyzed Oxidative Carbocyclization: Stereoselective Formation of C–C and C–B Bonds
Stockholm University, Faculty of Science, Department of Organic Chemistry.
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 [en]
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: urn:nbn:se:su:diva-108669ISBN: 978-91-7649-020-4 (print)OAI: oai:DiVA.org:su-108669DiVA: diva2:759895
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
List of papers
1. 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
2. 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
3. Palladium-Catalyzed Oxidative Diarylating Carbocyclization of Enynes
Open this publication in new window or tab >>Palladium-Catalyzed Oxidative Diarylating Carbocyclization of Enynes
2012 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 14, no 13, 3538-3541 p.Article in journal (Refereed) Published
Abstract [en]

A mild and efficient palladium-catalyzed oxidative diarylating carbocyclization of enynes is described. The reaction tolerates a range of functionalized arylboronic acids to give diarylated products in good yields. Control experiments suggest that the reaction starts with an arylpalladation of the alkyne, followed by carbocyclization, transmetalation, and reductive elimination to afford the diarylated product.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-86241 (URN)10.1021/ol301551x (DOI)000306050300077 ()
Funder
Swedish Research CouncilEU, European Research Council, ERC AdG247014
Available from: 2013-01-11 Created: 2013-01-11 Last updated: 2017-12-06Bibliographically approved
4. Palladium(II)/Bronsted Acid-Catalyzed Enantioselective Oxidative Carbocyclization-Borylation of Enallenes
Open this publication in new window or tab >>Palladium(II)/Bronsted Acid-Catalyzed Enantioselective Oxidative Carbocyclization-Borylation of Enallenes
Show others...
2015 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 54, no 20, 6024-6027 p.Article in journal (Refereed) Published
Abstract [en]

An enantioselective oxidative carbocyclization-borylation of enallenes that is catalyzed by palladium(II) and a Bronsted acid was developed. Biphenol-type chiral phosphoric acids were superior co-catalysts for inducing the enantioselective cyclization. A number of chiral borylated carbocycles were synthesized in high enantiomeric excess.

Keyword
carbocyclization, chiral anion, chiral phosphoric acid, oxidation, palladium
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-117774 (URN)10.1002/anie.201501048 (DOI)000354255400041 ()
Funder
EU, European Research CouncilSwedish Research CouncilBerzelii Centre EXSELENTKnut and Alice Wallenberg Foundation
Available from: 2015-06-05 Created: 2015-06-01 Last updated: 2017-12-04Bibliographically approved

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