CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Advances in Stereoselective Palladium(ΙΙ)-Catalyzed Oxidative Transformations of Allenes
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2020 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Palladium(ΙΙ)-catalyzed carbon-carbon and carbon-heteroatom bond formation via selective C-H bond oxidation constitutes a step-economical and versatile approach towards complex target molecules. This thesis has been focused on the development of new selective palladium(ΙΙ)-catalyzed transformations of allenes under oxidative conditions catalyzed by either homogenous or heterogeneous palladium(ΙΙ) catalysts.

The first part of this thesis describes carbocyclization-borylation of bisallenes, alkynylation of enallenes and preparation of [3]dendralenes from readily available allene starting materials. These homogenous palladium(ΙΙ)-catalyzed transformations involve selective allenic C-H cleavage under oxidative conditions. The aforementioned reactions can be carried out under aerobic biomimetic conditions by using electron transfer mediators (ETMs) and oxygen gas as the stoichiometric oxidant.

The second part deals with highly diastereoselective palladium-catalyzed oxidative carbocyclization reactions of enallenes assisted by weakly coordinating functional groups, such as hydroxyl or sulfonamide groups. It was demonstrated, that this weak coordination is sufficient to trigger the allene attack on the metal center enabling formation of (vinyl)Pd(II) intermediates, previously achievable by the directing effect of unsaturated hydrocarbon groups. A broad range of borylated cyclohexanol derivatives, as well as cis-fused [5,5] bicyclic γ-lactones and γ-lactams were obtained with superb diastereoselectivity via palladium(ΙΙ)-catalyzed carbocyclization-functionalization reactions of enallenols.

The final part of the thesis describes applications of the heterogenous catalyst Pd-AmP-MCF in oxidation reactions of allenes. Chemodivergent oxidative cascade reactions of enallenols were realized by switching between heterogeneous (Pd-AmP-MCF) and homogeneous (Pd(OAc)2) palladium catalysts. In separate cases, the heterogeneous catalyst Pd-AmP-MCF showed improved performance over its homogeneous counterpart, accompanied by high recyclability and no detectable metal leaching. Synthetically important cyclic skeletons such as cyclobutenols, furanes, oxaboroles, and fused γ-lactones/lactams were obtained via borylative or carbonylative carbocyclization reactions of enallenols in high yields and with excellent stereoselectivity.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University , 2020. , p. 96
Keywords [en]
Synthesis, Palladium Catalysis, Allenes, Biomimetic, Carbocyclization, Borylation, Carbonylation, Oxidation, Heterogeneous
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-180797ISBN: 978-91-7911-150-2 (print)ISBN: 978-91-7911-151-9 (electronic)OAI: oai:DiVA.org:su-180797DiVA, id: diva2:1423464
Public defence
2020-05-29, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Available from: 2020-05-06 Created: 2020-04-14 Last updated: 2020-06-01Bibliographically approved
List of papers
1. Selective Cascade Reaction of Bisallenes via Palladium-Catalyzed Aerobic Oxidative Carbocyclization-Borylation and Aldehyde Trapping
Open this publication in new window or tab >>Selective Cascade Reaction of Bisallenes via Palladium-Catalyzed Aerobic Oxidative Carbocyclization-Borylation and Aldehyde Trapping
2017 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 56, no 6, p. 1590-1594Article in journal (Refereed) Published
Abstract [en]

A cascade reaction, consisting of a palladium-catalyzed regioselective aerobic oxidative carbocyclization-borylation of bisallenes and a final aldehyde trapping, afforded triene alcohols with high diastereoselectivity. The cascade reaction occurs under mild reaction conditions and proceeds via an allylboron intermediate that is trapped by the aldehyde in a stereoselective manner.

Keywords
biomimetic oxidation, bisallene, cascade reaction, catalysis, palladium
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-141360 (URN)10.1002/anie.201610524 (DOI)000394998300026 ()28067015 (PubMedID)
Funder
Swedish Research CouncilWenner-Gren Foundations
Available from: 2017-05-02 Created: 2017-05-02 Last updated: 2020-04-17Bibliographically approved
2. Highly Selective Olefin-Assisted Pd-II-Catalyzed Oxidative Alkynylation of Enallenes
Open this publication in new window or tab >>Highly Selective Olefin-Assisted Pd-II-Catalyzed Oxidative Alkynylation of Enallenes
Show others...
2017 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 23, no 33, p. 7896-7899Article in journal (Refereed) Published
Abstract [en]

An olefin-assisted, palladium-catalyzed oxidative alkynylation of enallenes for regio- and stereoselective synthesis of substituted trienynes has been developed. The reaction shows a broad substrate scope and good tolerance for various functional groups on the allene moiety, including carboxylic acid esters, free hydroxyls, imides, and alkyl groups. Also, a wide range of terminal alkynes with electron-donating and electron-withdrawing aryls, heteroaryls, alkyls, trimethylsilyl, and free hydroxyl groups are tolerated.

Keywords
alkynylation, enallene, olefin-assisted, oxidation, palladium
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-145317 (URN)10.1002/chem.201701654 (DOI)000403150100011 ()28440882 (PubMedID)
Funder
Swedish Research CouncilBerzelii Centre EXSELENTKnut and Alice Wallenberg Foundation
Available from: 2017-07-25 Created: 2017-07-25 Last updated: 2020-04-17Bibliographically approved
3. Selective Palladium-Catalyzed Allenic C-H Bond Oxidation for the Synthesis of [3]Dendralenes
Open this publication in new window or tab >>Selective Palladium-Catalyzed Allenic C-H Bond Oxidation for the Synthesis of [3]Dendralenes
2017 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 56, no 42, p. 13112-13116Article in journal (Refereed) Published
Abstract [en]

A highly selective palladium-catalyzed allenic C-H bond oxidation was developed, and it provides a novel and straightforward synthesis of [3]dendralene derivatives. A variety of [3]dendralenes with diverse substitution patterns are accessible with good efficiency and high stereoselectivity. The reaction tolerates a broad substrate scope containing various functional groups on the allene moiety, including ketone, aldehyde, ester, and phenyl groups. Also, a wide range of olefins with both electron-donating and electron-withdrawing aryls, acrylate, sulfone, and phosphonate groups are tolerated.

Keywords
dendralenes, allenes, olefination, palladium, regioselectivity
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-147910 (URN)10.1002/anie.201706211 (DOI)000412189700058 ()28799682 (PubMedID)
Funder
EU, European Research CouncilSwedish Research CouncilBerzelii Centre EXSELENTKnut and Alice Wallenberg Foundation
Available from: 2017-10-17 Created: 2017-10-17 Last updated: 2020-04-17Bibliographically approved
4. Highly Diastereoselective Palladium-Catalyzed Oxidative Carbocyclization of Enallenes Assisted by a Weakly Coordinating Hydroxyl Group
Open this publication in new window or tab >>Highly Diastereoselective Palladium-Catalyzed Oxidative Carbocyclization of Enallenes Assisted by a Weakly Coordinating Hydroxyl Group
2018 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 140, no 9, p. 3210-3214Article in journal (Refereed) Published
Abstract [en]

A highly diastereoselective palladium-catalyzed oxidative carbocyclization-borylation of enallenes assisted by a weakly coordinating hydroxyl group was developed. The reaction afforded functionalized cyclo-hexenol derivatives, in which the 1,3-relative stereo chemistry is controlled (d.r. > 50:1). Other weakly coordinating oxygen-containing groups (ketone, alkoxide, acetate) also assisted the carbocyclization toward cyclo-hexenes. The reaction proceeds via a ligand exchange on Pd of the weakly coordinating group with a distant olefin group. The high diastereoselectivity of the hydroxyl directed reaction could be rationalized by a face-selective coordination of the distant olefin. It was demonstrated that the primary coordination of the close-by oxygen containing functionality was necessary for the reaction to occur and removal of this functionality shut down the reaction.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-156114 (URN)10.1021/jacs.7b13563 (DOI)000427203600010 ()29425445 (PubMedID)
Available from: 2018-05-07 Created: 2018-05-07 Last updated: 2020-04-17Bibliographically approved
5. Highly Diastereoselective Palladium-Catalyzed Oxidative Cascade Carbonylative Carbocyclization of Enallenols
Open this publication in new window or tab >>Highly Diastereoselective Palladium-Catalyzed Oxidative Cascade Carbonylative Carbocyclization of Enallenols
Show others...
2020 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 22, no 2, p. 417-421Article in journal (Refereed) Published
Abstract [en]

A palladium-catalyzed oxidative cascade carbonylative carbocyclization of enallenols was developed. Under mild reaction conditions, a range of cis-fused [5,5] bicyclic gamma-lactones and gamma-lactams with a 1,3-diene motif were obtained in good yields with high diastereoselectivity. The obtained lactone/lactam products are viable substrates for a stereoselective Diels-Alder reaction with N-phenylmaleimide, providing polycyclic compounds with increased molecular complexity.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-179627 (URN)10.1021/acs.orglett.9b04134 (DOI)000508468200016 ()31895577 (PubMedID)
Available from: 2020-03-16 Created: 2020-03-16 Last updated: 2020-04-17Bibliographically approved
6. Diastereoselective Cyclobutenol Synthesis: A Heterogeneous Palladium-Catalyzed Oxidative Carbocyclization-Borylation of Enallenols
Open this publication in new window or tab >>Diastereoselective Cyclobutenol Synthesis: A Heterogeneous Palladium-Catalyzed Oxidative Carbocyclization-Borylation of Enallenols
Show others...
2019 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 25, no 1, p. 210-215Article in journal (Refereed) Published
Abstract [en]

A highly selective and efficient oxidative carbocyclization/borylation of enallenols catalyzed by palladium immobilized on amino-functionalized siliceous mesocellular foam (Pd-AmP-MCF) was developed for diastereoselective cyclobutenol synthesis. The heterogeneous palladium catalyst can be recovered and recycled without any observed loss of activity or selectivity. The high diastereoselectivity of the reaction is proposed to originate from a directing effect of the enallenol hydroxyl group. Optically pure cyclobutenol synthesis was achieved by the heterogeneous strategy by using chiral enallenol obtained from kinetic resolution.

Keywords
cyclobutenols, diastereoselectivity, enallenols, heterogeneous catalysis, oxidative carbocyclization, palladium
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-165694 (URN)10.1002/chem.201805118 (DOI)000454705500025 ()30307089 (PubMedID)
Available from: 2019-02-05 Created: 2019-02-05 Last updated: 2020-04-17Bibliographically approved
7. Chemodivergent and Diastereoselective Synthesis of gamma-Lactones and gamma-Lactams: A Heterogeneous Palladium-Catalyzed Oxidative Tandem Process
Open this publication in new window or tab >>Chemodivergent and Diastereoselective Synthesis of gamma-Lactones and gamma-Lactams: A Heterogeneous Palladium-Catalyzed Oxidative Tandem Process
Show others...
2018 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 140, no 44, p. 14604-14608Article in journal (Refereed) Published
Abstract [en]

A palladium-catalyzed oxidative tandem process of enallenols was accomplished within a homogeneous/heterogeneous catalysis manifold, setting the stage for the highly chemodivergent and diaster-eoselective synthesis of gamma-lactones and gamma-lactams under mild conditions.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-162860 (URN)10.1021/jacs.8b09562 (DOI)000449887800017 ()30358399 (PubMedID)
Available from: 2018-12-28 Created: 2018-12-28 Last updated: 2020-05-09Bibliographically approved
8. Efficient Heterogeneous Palladium-Catalyzed Oxidative Cascade Reactions of Enallenols to Furan and Oxaborole Derivatives
Open this publication in new window or tab >>Efficient Heterogeneous Palladium-Catalyzed Oxidative Cascade Reactions of Enallenols to Furan and Oxaborole Derivatives
Show others...
2020 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 59, no 5, p. 1992-1996Article in journal (Refereed) Published
Abstract [en]

A heterogeneous palladium-catalyzed oxidative cyclization of enallenols has been developed for the construction of highly substituted furan and oxaborole derivatives. The heterogeneous catalyst (Pd-AmP-MCF) exhibits high activity, high site- and stereoselectivity, and efficient palladium recyclability in the transformations.

Keywords
efficiency, heterogeneous palladium, oxidative cyclizations, stereospecific
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-177450 (URN)10.1002/anie.201911462 (DOI)000502398300001 ()31729824 (PubMedID)
Available from: 2020-01-22 Created: 2020-01-22 Last updated: 2020-04-17Bibliographically approved

Open Access in DiVA

Advances in Stereoselective Palladium(ΙΙ)-Catalyzed Oxidative Transformations of Allenes(6733 kB)19 downloads
File information
File name FULLTEXT01.pdfFile size 6733 kBChecksum SHA-512
04836df558fa5e68aba985f45268ca9d01222131aca0d92914a4c18998b6219234efa719e988f8086406cc6649e3e8307f7b55c66c483d68856023712796a6e4
Type fulltextMimetype application/pdf
Errata to Advances in Stereoselective Palladium(ΙΙ)-Catalyzed Oxidative Transformations of Allenes(170 kB)0 downloads
File information
File name ERRATA01.pdfFile size 170 kBChecksum SHA-512
07352bbe94aefeba6395a2503847d9881cc090cba091b249dcef40c3c63e5da1d60a35b4031693f1b94dd48607652059b4ec1c35b1ab8e0566e6058845a7f17b
Type errataMimetype application/pdf

Search in DiVA

By author/editor
Posevins, Daniels
By organisation
Department of Organic Chemistry
Organic Chemistry

Search outside of DiVA

GoogleGoogle Scholar
Total: 19 downloads
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

isbn
urn-nbn

Altmetric score

isbn
urn-nbn
Total: 119 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf