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Palladium-Catalyzed Synthesis and Transformations of Organometallic Compounds
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Responsible organisation
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 [en]
palladium
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-804ISBN: 91-7155-182-4 (print)OAI: oai:DiVA.org:su-804DiVA: diva2:199477
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
List of papers
1. Regioselective Palladium-Catalyzed Electrophilic Allylic Substitution in the Presence of Hexamethylditin
Open this publication in new window or tab >>Regioselective Palladium-Catalyzed Electrophilic Allylic Substitution in the Presence of Hexamethylditin
2002 In: Organic letters, ISSN 1523-7060, Vol. 4, no 9, 1563-1566 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-25320 (URN)
Note
Part of urn:nbn:se:su:diva-804Available from: 2006-01-18 Created: 2006-01-18Bibliographically approved
2. Palladium-Catalyzed Electrophilic Allylic Substitution of Allyl Chlorides and Acetates via Bis-allylpalladium Intermediates
Open this publication in new window or tab >>Palladium-Catalyzed Electrophilic Allylic Substitution of Allyl Chlorides and Acetates via Bis-allylpalladium Intermediates
2003 In: Journal of Organic Chemistry, ISSN 0022-3263, Vol. 68, no 7, 2934-2943 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-25321 (URN)
Note
Part of urn:nbn:se:su:diva-804Available from: 2006-01-18 Created: 2006-01-18Bibliographically approved
3. Origin of the Regio- and Stereoselectivity in Palladium-Catalyzed Electrophilic Substitution via Bis-allylpalladium Complexes
Open this publication in new window or tab >>Origin of the Regio- and Stereoselectivity in Palladium-Catalyzed Electrophilic Substitution via Bis-allylpalladium Complexes
2003 In: Chemistry : a European journal, ISSN 0947-6539, Vol. 9, no 17, 4025-4030 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-25322 (URN)
Note
Part of urn:nbn:se:su:diva-804Available from: 2006-01-18 Created: 2006-01-18Bibliographically approved
4. Palladium-Catalyzed Coupling of Allyl Acetates with Aldehyde and Imine Electrophiles in the Presence of Bis(pinacolato)diboron
Open this publication in new window or tab >>Palladium-Catalyzed Coupling of Allyl Acetates with Aldehyde and Imine Electrophiles in the Presence of Bis(pinacolato)diboron
2003 In: Organic Letters, ISSN 1523-7060, Vol. 5, no 17, 3065-3068 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-25323 (URN)
Note
Part of urn:nbn:se:su:diva-804Available from: 2006-01-18 Created: 2006-01-18Bibliographically approved
5. Palladium Pincer Complex-Catalyzed Allylic Stannylation with Hexaalkylditin Reagents
Open this publication in new window or tab >>Palladium Pincer Complex-Catalyzed Allylic Stannylation with Hexaalkylditin Reagents
2004 In: Organic Letters, ISSN 1523-7060, Vol. 6, no 11, 1829-1831 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-25324 (URN)
Note
Part of urn:nbn:se:su:diva-804Available from: 2006-01-18 Created: 2006-01-18Bibliographically approved
6. Palladium Pincer-Complex Catalyzed Allylation of Tosylimines by Potassium Trifluoro(allyl)borates
Open this publication in new window or tab >>Palladium Pincer-Complex Catalyzed Allylation of Tosylimines by Potassium Trifluoro(allyl)borates
2005 In: Organic letters, ISSN 1523-7060, Vol. 7, no 4, 689-691 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-25325 (URN)
Note
Part of urn:nbn:se:su:diva-804Available from: 2006-01-18 Created: 2006-01-18Bibliographically 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
8. Employment of Palladium Pincer-Complexes in Phenylselenylation of Organohalides
Open this publication in new window or tab >>Employment of Palladium Pincer-Complexes in Phenylselenylation of Organohalides
2005 In: Journal of Organic Chemistry, ISSN 0022-3263, Vol. 70, no 23, 9215-9221 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-25327 (URN)
Note
Part of urn:nbn:se:su:diva-804Available from: 2006-01-18 Created: 2006-01-18Bibliographically approved
9. Palladium Pincer Complex Catalyzed Cross-Coupling of Vinyl Epoxides and Aziridines with Organoboronic Acids
Open this publication in new window or tab >>Palladium Pincer Complex Catalyzed Cross-Coupling of Vinyl Epoxides and Aziridines with Organoboronic Acids
Show others...
2005 (English)In: Chemistry : a European journal, ISSN 0947-6539, Vol. 11, no 18, 5260-5268 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-25328 (URN)10.1002/chem.200500270 (DOI)
Note
Part of urn:nbn:se:su:diva-804Available from: 2006-01-18 Created: 2006-01-18 Last updated: 2009-05-25Bibliographically approved

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