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Catalytic Functionalization of Allylic Substrates by Palladium Pincer Complexes
Stockholm University, Faculty of Science, Department of Organic Chemistry. (Prof. Kálmán J. Szabó)
2010 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis is based on the development of novel catalytic reactions for the synthesis and application of organometallic reagents. The main focus is directed towards organoboronate derivatives. We developed an efficient procedure for converting allylic alcohols to the corresponding allylboronates using palladium pincer complexes as catalysts. The reactions were performed under mild conditions with high selectivity, allowing further one-pot transformations. Using this approach, a variety of stereodefined homoallylic alcohols and amino acid derivatives were synthesized via trapping of the in situ generated allylboronate derivatives with an appropriate electrophile. The synthetic scope of these types of multi-component reactions is broad as many different substrate allylic alcohols may be used together with various electrophiles. Several aspects of these reactions were studied, including different reagents, catalysts and electrophiles.

Furthermore, we studied the possibility to use oxidizing reagents as an essential component in the functionalization of olefins. Two main strategies were utilized for these catalytic methods using palladium pincer complexes. The functional group was either transferred from the oxidizing reagent, or introduced via an oxidation-transmetallation route. We propose that both methods involve palladium(IV) intermediates thus expanding both the coordination sphere of palladium and the synthetic scope of pincer complex catalysis.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University , 2010. , 65 p.
Keyword [en]
Catalysis, Palladium, Pincer Complex, Boron, Multicomponent Reaction
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-39065ISBN: 978-91-7447-090-1 (print)OAI: oai:DiVA.org:su-39065DiVA: diva2:318329
Public defence
2010-06-22, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 13:00 (English)
Opponent
Supervisors
Note
At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 11: In press.Available from: 2010-05-24 Created: 2010-05-06 Last updated: 2010-05-21Bibliographically approved
List of papers
1. Pincer complex-catalyzed redox coupling of alkenes with iodonium salts via presumed palladium(IV) intermediates
Open this publication in new window or tab >>Pincer complex-catalyzed redox coupling of alkenes with iodonium salts via presumed palladium(IV) intermediates
2009 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 11, no 13, 2852-2854 p.Article in journal (Refereed) Published
Abstract [en]

Palladium pincer complexes directly catalyze the redox coupling reactions of functionalized alkenes and iodonium salts. The catalytic process, which is suitable for mild catalytic functionalization of allylic acetates and electron-rich alkenes, probably occurs through Pd(IV) intermediates. Due to the strong metal−ligand interactions, the oxidation of phosphine and amine ligands of the pincer complexes can be avoided in the presented reactions.

Place, publisher, year, edition, pages
American Chemical Society, 2009
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-29393 (URN)10.1021/ol9010739 (DOI)000267400100035 ()
Available from: 2009-08-26 Created: 2009-08-26 Last updated: 2013-05-02Bibliographically approved
2. Direct synthesis of functionalized allylic boronic esters from allylic alcohols and inexpensive reagents and catalysts
Open this publication in new window or tab >>Direct synthesis of functionalized allylic boronic esters from allylic alcohols and inexpensive reagents and catalysts
2008 (English)In: Synthesis (Stuttgart), ISSN 0039-7881, E-ISSN 1437-210X, no 14, 2293-2297 p.Article in journal (Refereed) Published
Abstract [en]

A remarkably simple and effective system for the direct conversion of allylic alcohols into high value allylic boronic esters using commercially available reagents and catalysts is described.

Keyword
allylation, palladium, palladacycles, transition metal
Identifiers
urn:nbn:se:su:diva-14906 (URN)10.1055/s-2008-1067144 (DOI)000258224600021 ()
Available from: 2008-12-03 Created: 2008-12-03 Last updated: 2010-05-21Bibliographically approved
3. Petasis borono-Mannich reaction and allylation of carbonyl compounds via transient allyl boronates generated by palladium-catalyzed substitution of allyl alcohols: An efficient one-pot route to stereodefined alpha-amino acids and homoallyl alcohols
Open this publication in new window or tab >>Petasis borono-Mannich reaction and allylation of carbonyl compounds via transient allyl boronates generated by palladium-catalyzed substitution of allyl alcohols: An efficient one-pot route to stereodefined alpha-amino acids and homoallyl alcohols
2007 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 129, no 44, 13723-13731 p.Article in journal (Refereed) Published
Abstract [en]

An efficient one-pot procedure was designed by integration of the pincer-complex-catalyzed borylation of allyl alcohols in the Petasis borono-Mannich reaction and in allylation of aldehydes and ketones. These procedures are suitable for one-pot synthesis of α-amino acids and homoallyl alcohols from easily available allyl alcohol, amine, aldehyde, or ketone substrates. In the presented transformations, the active allylating agents are in situ generated allyl boronic acid derivatives. These transient intermediates are proved to be reasonably acid-, base-, alcohol-, water-, and air-stable species, which allows a high level of compatibility with the reaction conditions of the allylation of various aldehyde/ketone and imine electrophiles. The boronate source of the reaction is diboronic acid or in situ hydrolyzed diboronate ester ensuring that the waste product of the reaction is nontoxic boric acid. The regio- and stereoselectivity of the reaction is excellent, as almost all products form as single regio- and stereoisomers. The described procedure is suitable to create quaternary carbon centers in branched allylic products without formation of the corresponding linear allylic isomers. Furthermore, products comprising three stereocenters were formed as single products without formation of other diastereomers. Because of the highly disciplined consecutive processes, up to four-step, four-component transformations could be performed selectively as a one-pot sequence. For example, stereodefined pyroglutamic acid could be prepared from a simple allyl alcohol, a commercially available amine, and glyoxylic acid in a one-step procedure. The presented method also grants an easy access to stereodefined 1,7-dienes that are useful substrates for Grubbs ring-closing metathesis.

Identifiers
urn:nbn:se:su:diva-19692 (URN)10.1021/ja074917a (DOI)000250819200060 ()
Available from: 2007-11-15 Created: 2007-11-15 Last updated: 2010-05-21Bibliographically approved
4. Performance of SCS palladium pincer complexes in borylation of allylic alcohols. Control of the regioselectivity in the one-pot borylation-allylation process
Open this publication in new window or tab >>Performance of SCS palladium pincer complexes in borylation of allylic alcohols. Control of the regioselectivity in the one-pot borylation-allylation process
2009 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 74, no 15, 5695-5698 p.Article in journal (Refereed) Published
Abstract [en]

One-pot borylation−allylation reactions of aldehydes and allylic alcohols were performed under various reaction conditions. The borylation of allylic alcohols was performed using a very efficient SCS palladium pincer-complex catalyst. The regioselectivity of the allylation depends on the applied solvent. The reaction in CHCl3 gave the linear allylic product; however, when MeOH was added to the reaction mixture, the branched allylic product was formed.

Place, publisher, year, edition, pages
American Chemical Society, 2009
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-31751 (URN)10.1021/jo9008673 (DOI)000268480300090 ()
Available from: 2009-11-26 Created: 2009-11-26 Last updated: 2010-05-21Bibliographically approved
5. Catalytic allylic C—H acetoxylation and benzoyloxylation via suggested (η3-allyl)palladium(IV) intermediates
Open this publication in new window or tab >>Catalytic allylic C—H acetoxylation and benzoyloxylation via suggested (η3-allyl)palladium(IV) intermediates
2009 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 11, no 23, 5518-5521 p.Article in journal (Refereed) Published
Abstract [en]

Palladium-catalyzed allylic acetoxylations and benzoyloxylations were carried out using iodonium salts. The reactions proceed under mild conditions with high regio- and stereoselectivity. The catalysis can be performed under both acidic and nonacidic conditions without use of BQ or other external oxidants and activator ligands. Deuterium labeling experiments clearly show that the catalytic reaction proceeds through (η3-allyl)palladium intermediates. A stoichiometric study with one of the catalysts provided evidence for the formation of a Pd(IV) species.

Place, publisher, year, edition, pages
American Chemical Society, 2009
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-32430 (URN)10.1021/ol9023369 (DOI)000272038200040 ()
Available from: 2009-12-10 Created: 2009-12-10 Last updated: 2010-05-21Bibliographically approved
6. Synthesis of stereodefined substituted cycloalkenes by a one-pot catalytic boronation-allylation-metathesis sequence
Open this publication in new window or tab >>Synthesis of stereodefined substituted cycloalkenes by a one-pot catalytic boronation-allylation-metathesis sequence
2008 (English)In: Advanced Synthesis and Catalysis, ISSN 1615-4150, E-ISSN 1615-4169, Vol. 350, no 13, 2045-2051 p.Article in journal (Refereed) Published
Abstract [en]

Stereodefined cyclohexene and cyclopentene derivatives were prepared by the coupling of allylic alcohols and other allylic precursors with unsaturated aldehydes. These reactions are based on a multicatalytic one-pot approach involving palladium pincer complex-catalyzed boronation, allylation and ring-closing metathesis reactions. This reaction sequence can be performed in an operationally simple procedure affording the cycloalkene products in high overall yields and excellent regio- and stereoselectivities. The presented procedure has a broad synthetic scope and high functional group tolerance, which allows the synthesis of bicyclic lactone and spirane skeletons and various substitution patterns including hydroxy, silyl, vinyl, allyl, and sulfonyl groups. The studied catalytic one-pot reactions involve up to three individual processes performed by up to four acid- and transition metal-catalyzed events.

Keyword
allylation, boronation, homogenous catalysis, metathesis, palladium pincer complexes, stereoselectivity
Identifiers
urn:nbn:se:su:diva-14905 (URN)10.1002/adsc.200800324 (DOI)000259544300020 ()
Available from: 2009-01-02 Created: 2009-01-02 Last updated: 2010-05-21Bibliographically approved
7. Single-pot triple catalytic transformations based on coupling of in situ generated allyl boronates with in situ hydrolyzed acetals
Open this publication in new window or tab >>Single-pot triple catalytic transformations based on coupling of in situ generated allyl boronates with in situ hydrolyzed acetals
2008 (English)In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, no 29, 3420-3422 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-14909 (URN)10.1039/b804920c (DOI)000257722700021 ()
Available from: 2009-01-02 Created: 2009-01-02 Last updated: 2010-05-21Bibliographically approved
8. 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: 2010-05-21Bibliographically approved
9. Strategies for fine-tuning the catalytic activity of pincer-complexes
Open this publication in new window or tab >>Strategies for fine-tuning the catalytic activity of pincer-complexes
2006 (English)In: Tetrahedron Letters, ISSN 0040-4039, E-ISSN 1873-3581, Vol. 47, no 50, 8999-9001 p.Article in journal (Refereed) Published
Abstract [en]

Various methoxy substituted pincer-complexes were prepared in order to study the substituent effects on the catalytic activity in palladium catalyzed opening of vinyl epoxides and boronation of cinnamyl alcohol. The results clearly show that methoxy substitution at the para-position of the pincer-complex leads to up to fourfold acceleration of the catalytic reactions, while substitution of the side-arms does not change the activity of the complex or leads to a slight deceleration of the catalytic processes.

Keyword
Pincer-complexes; Catalysis; Substituent effects; Palladium; Boron; Epoxide
Identifiers
urn:nbn:se:su:diva-25750 (URN)10.1016/j.tetlet.2006.08.141 (DOI)
Note
Part of urn:nbn:se:su:diva-8524Available from: 2009-02-26 Created: 2009-02-17 Last updated: 2010-05-21Bibliographically approved
10. Highly Selective and Robust Palladium-Catalysed Carbon-Carbon Coupling between Allyl Alcohols and Aldehydes via Transient Allylboronic Acids
Open this publication in new window or tab >>Highly Selective and Robust Palladium-Catalysed Carbon-Carbon Coupling between Allyl Alcohols and Aldehydes via Transient Allylboronic Acids
2006 (English)In: European Journal of Organic Chemistry, ISSN 1434-193X, E-ISSN 1099-0690, no 18, 4085-4087 p.Article in journal (Refereed) Published
Abstract [en]

The highly regio- and stereoselective coupling of allyl alcohols with aldehydes could be achieved with 5 mol-% of SeCSe pincer complex catalyst and p-toluenesulfonic acid in the presence of diboronic acid. The transformations have a broad synthetic scope, and the high yields were obtained without the use of an inert atmosphere and carefully dried solvents.

Place, publisher, year, edition, pages
Weinheim: WILEY-VCH, 2006
Keyword
Aldehydes, Allylation, Boron, Electrophilic substitution, Palladium
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-39078 (URN)10.1002/ejoc.200600530 (DOI)
Available from: 2010-05-07 Created: 2010-05-07 Last updated: 2010-05-21Bibliographically approved
11. Selective C-H Borylation of Alkenes by Palladium Pincer Complex Catalyzed Oxidative Functionalization
Open this publication in new window or tab >>Selective C-H Borylation of Alkenes by Palladium Pincer Complex Catalyzed Oxidative Functionalization
2010 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 49, no 24, 4051-4053 p.Article in journal (Refereed) Published
Place, publisher, year, edition, pages
Weinheim: Wiley-VCH Verlagsgesellschaft, 2010
Keyword
alkenes, boron, C-H activation, hypervalent compounds, palladium
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-39080 (URN)10.1002/anie.201000690 (DOI)000278796400008 ()
Available from: 2010-05-07 Created: 2010-05-07 Last updated: 2011-12-05Bibliographically approved

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