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Synthesis of New Chiral Pincer-Complex Catalysts for Asymmetric Allylation of Sulfonimines
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Responsible organisation
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.

Place, publisher, year, edition, pages
2006. Vol. 359, no 6, 1767-1772 p.
Identifiers
URN: urn:nbn:se:su:diva-25326DOI: 10.1016/j.ica.2005.06.059OAI: oai:DiVA.org:su-25326DiVA: diva2:199474
Note
Part of urn:nbn:se:su:diva-804Available from: 2006-01-18 Created: 2006-01-18 Last updated: 2017-12-13Bibliographically approved
In thesis
1. Palladium-Catalyzed Synthesis and Transformations of Organometallic Compounds
Open this publication in new window or tab >>Palladium-Catalyzed Synthesis and Transformations of Organometallic Compounds
2006 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis is focused on two important fields of palladium catalysis: the development of electrophilic allylic substitution reactions via bis-allylpalladium intermediates; and application of palladium pincer-complexes in the synthesis and transformations of organometallic compounds.

Palladium-catalyzed electrophilic allylation of aldehyde and imine substrates could be achieved using readily available allyl chlorides and acetates by employing hexamethylditin or bis(pinacolato)diboron reagents. The reaction proceeds under mild and neutral reaction conditions with high regioselectivity, providing the branched homoallylic products. The stereoselectivity of the reaction depends on the steric and electronic effects of the allylic substituents of the substrates. DFT modeling of the electrophilic attack on the bis-allylpalladium intermediate of the reaction revealed the origin of the regio- and stereoselectivity of the reaction.

Palladium pincer-complexes were employed as catalysts in a variety of reactions such as stannylation, selenylation, allylation, and cross coupling reactions with various electrophiles. Allylic stannylation in the presence of hexamethylditin was achieved by use of an NCN palladium pincer-complex catalyst. In contrast to the reactions catalyzed by traditional palladium catalysts, isolation of functionalized allyl stannanes was possible due to the special features of the pincer-complex catalyst. Extension of the scope of the palladium pincer-complex catalyzed electrophilic allylation reactions was achieved by using potassium trifluoro(allyl)borate instead of allyl stannanes. In addition, asymmetric electrophilic allylation of sulfonimines was achieved by employment of novel BINOL-based palladium pincer-complexes. The enantioselectivity of the pincer-complex catalyst was fine-tuned by employment of substituted analogs of BINOL.

Place, publisher, year, edition, pages
Stockholm: Institutionen för organisk kemi, 2006. 43 p.
Keyword
palladium
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-804 (URN)91-7155-182-4 (ISBN)
Public defence
2006-02-09, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 14:00
Opponent
Supervisors
Available from: 2006-01-18 Created: 2006-01-18Bibliographically approved
2. Development of New Synthetic Routes to Organoboronates by Catalytic Allylic Substitution and C-H bond Functionalization
Open this publication in new window or tab >>Development of New Synthetic Routes to Organoboronates by Catalytic Allylic Substitution and C-H bond Functionalization
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
Palladium, Iridium, Boron, Catalysis
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-27753 (URN)978-91-7155-899-2 (ISBN)
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

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