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Development of New Synthetic Routes to Organoboronates by Catalytic Allylic Substitution and C-H bond Functionalization
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2009 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis describes the development of new catalytic methods for the synthesis and application of organometallic reagents, mainly focusing on allylboronic acid derivatives. Thus, palladium pincer-complex catalysis has been applied for extending the scope of palladiumcatalyzed borylation reactions in the synthesis of regio- and stereodefined functionalized allylboronic acid derivatives. These novel allylboronic acids were also employed as substrates in palladium catalyzed regioselective coupling reactions with iodobenzenes. We have also developed a new one-pot sequence based on preparation of allyl- and vinylboronates

via catalytic carbon-hydrogen bond activation/borylation reactions. The synthetic scope of the reaction as well as mechanistic studies on the borylation process are presented. Finally, the synthesis of new chiral palladium pincer-complexes is described. These species were employed as catalysts in asymmetric electrophilic allyation of imines.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University , 2009. , 54 p.
Keyword [en]
Palladium, Iridium, Boron, Catalysis
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-27753ISBN: 978-91-7155-899-2 (print)OAI: oai:DiVA.org:su-27753DiVA: diva2:217751
Public defence
2009-06-11, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 13:00 (English)
Opponent
Supervisors
Available from: 2009-05-20 Created: 2009-05-15 Last updated: 2009-05-19Bibliographically approved
List of papers
1. Palladium Pincer Complex Catalyzed Substitution of Vinyl Cyclopropanes, Vinyl Aziridines, and Allyl Acetates with Tetrahydroxydiboron. An Efficient Route to Functionalized Allylboronic Acids and Potassium Trifluoro(allyl)borates
Open this publication in new window or tab >>Palladium Pincer Complex Catalyzed Substitution of Vinyl Cyclopropanes, Vinyl Aziridines, and Allyl Acetates with Tetrahydroxydiboron. An Efficient Route to Functionalized Allylboronic Acids and Potassium Trifluoro(allyl)borates
2005 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 127, no 30, 10478-10479 p.Article in journal (Refereed) Published
Abstract [en]

Palladium-catalyzed boronation of vinyl cyclopropane, vinyl aziridine, and allyl acetate substrates could be accomplished using tetrahydroxydiboron reagent in the presence of SeCSe pincer complex catalyst 1a. These reactions result in allyl boronic acids, which were converted to synthetically useful trifluoro(allyl)borates or allyl boronates. The catalytic transformations proceed under mild and neutral conditions, and therefore many functionalities Br, COOEt, ArSO2(NH), OAc, and SiRMe2 are tolerated. The selectivity of the presented processes is very high, affording the linear products incorporating a trans double bond.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-27801 (URN)10.1021/ja052885q (DOI)
Available from: 2009-05-19 Created: 2009-05-19 Last updated: 2017-12-13Bibliographically approved
2. Direct Boronation of Allyl Alcohols with Diboronic Acid Using Palladium Pincer-Complex Catalysis. A Remarkably Facile Allylic Displacement of the Hydroxy Group under Mild Reaction Conditions
Open this publication in new window or tab >>Direct Boronation of Allyl Alcohols with Diboronic Acid Using Palladium Pincer-Complex Catalysis. A Remarkably Facile Allylic Displacement of the Hydroxy Group under Mild Reaction Conditions
2006 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 128, no 14, 4588-4589 p.Article in journal (Refereed) Published
Abstract [en]

Allyl alcohols were converted to allyl boronic acids and subsequently to trifluoro(allyl)borates with tetrahydroxy diboron using palladium pincer-complex catalysis. These reactions are regio- and stereoselective proceeding with high isolated yields. Competitive boronation experiments indicate that under the applied reaction conditions the allylic displacement of a hydroxy group is faster than the displacement of an acetate leaving group. It is assumed that the hydroxy group of the allyl alcohol is converted to a diboronic acid ester functionality, which can easily be substituted.

National Category
Other Basic Medicine
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-27749 (URN)10.1021/ja060468n (DOI)
Available from: 2009-05-15 Created: 2009-05-15 Last updated: 2017-12-13Bibliographically approved
3. Palladium-Catalyzed Coupling of Allylboronic Acids with Iodobenzenes. Selective Formation of the Branched Allylic Product in the Absence of Directing Groups
Open this publication in new window or tab >>Palladium-Catalyzed Coupling of Allylboronic Acids with Iodobenzenes. Selective Formation of the Branched Allylic Product in the Absence of Directing Groups
2006 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 128, no 25, 8150-8151 p.Article in journal (Refereed) Published
Abstract [en]

Palladium-catalyzed coupling reactions of functionalized allylboronic acids with iodobenzenes were achieved under standard Suzuki−Miyaura coupling conditions. The coupling reactions afforded selectively the branched allylic products in high to excellent yields. In contrast to palladium-catalyzed nucleophilic substitution reactions proceeding via (η3-allyl)palladium intermediates, this process does not require directing groups in the allyl moiety to achieve substitution at the congested allylic terminus. The regioselectivity of the process was largely unaffected by the substituent effects of the iodobenzenes and the allylic substrates.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-27802 (URN)10.1021/ja062585o (DOI)
Available from: 2009-05-19 Created: 2009-05-19 Last updated: 2017-12-13Bibliographically approved
4. Selective one-pot carbon-carbon bond formation by catalytic boronation of unactivated cycloalkenes and subsequent coupling
Open this publication in new window or tab >>Selective one-pot carbon-carbon bond formation by catalytic boronation of unactivated cycloalkenes and subsequent coupling
2007 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 46, no 36, 6891-6893 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-19691 (URN)10.1002/anie.200702499 (DOI)000249569200034 ()
Available from: 2007-11-15 Created: 2007-11-15 Last updated: 2017-12-13Bibliographically approved
5. Synthesis of allylsilanes and dienylsilanes by a one-pot catalytic C-H borylation-Suzuki-Miyaura coupling sequence
Open this publication in new window or tab >>Synthesis of allylsilanes and dienylsilanes by a one-pot catalytic C-H borylation-Suzuki-Miyaura coupling sequence
2008 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 10, no 14, 3129-3131 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-14907 (URN)10.1021/ol801203u (DOI)000257629200054 ()
Available from: 2009-01-02 Created: 2009-01-02 Last updated: 2017-12-13Bibliographically approved
6. Functionalization of Unactivated Alkenes trough Iridium-Catalyzed Borylation of Carbon-Hydrogen Bonds. Mechanism and Synthetic Applications
Open this publication in new window or tab >>Functionalization of Unactivated Alkenes trough Iridium-Catalyzed Borylation of Carbon-Hydrogen Bonds. Mechanism and Synthetic Applications
(English)Manuscript (Other academic)
National Category
Other Basic Medicine
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-27752 (URN)
Available from: 2009-05-15 Created: 2009-05-15 Last updated: 2010-01-14Bibliographically approved
7. Synthesis of New Chiral Pincer-Complex Catalysts for Asymmetric Allylation of Sulfonimines
Open this publication in new window or tab >>Synthesis of New Chiral Pincer-Complex Catalysts for Asymmetric Allylation of Sulfonimines
2006 (English)In: Inorganica Chimica Acta, ISSN 0020-1693, E-ISSN 1873-3255, Vol. 359, no 6, 1767-1772 p.Article in journal (Refereed) Published
Abstract [en]

Four new chiral pincer-complexes were prepared based on coupling of BINOL and TADDOL moieties with iodoresorcinol followed by oxidative addition of palladium(0). The X-ray analysis of complex 5a revealed that the BINOL rings form a well-defined chiral pocket around the palladium atom. This chiral environment can be further modified by γ-substitution of the BINOL rings. Preliminary studies for electrophilic allylation of sulfonimine 2 with allylstannane revealed that the presented chiral complexes are promising asymmetric catalysts for preparation of chiral homoallyl amines. The best result was achieved employing catalytic amounts of γ-Me BINOL complex 6 affording homoallyl amine 4 with 59% ee and 74% isolated yield.

Identifiers
urn:nbn:se:su:diva-25326 (URN)10.1016/j.ica.2005.06.059 (DOI)
Note
Part of urn:nbn:se:su:diva-804Available from: 2006-01-18 Created: 2006-01-18 Last updated: 2017-12-13Bibliographically approved

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