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Control of the Regioselectivity in Catalytic Transformations Involving Amphiphilic Bis-allylpalladium Intermediates: Mechanism and Synthetic Applications
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.ORCID-id: 0000-0002-9349-7137
2001 (Engelska)Ingår i: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 66, nr 5, s. 1686-1693Artikel i tidskrift (Refereegranskat) Published
Abstract [en]

Various dialkyl-substituted allyl chloride derivatives (2d−i) undergo regioselective palladium-catalyzed coupling reactions with allylstannanes (1a,b) and benzylidenemalonitrile (4), providing functionalized 1,7-octadienes in good yield. The catalytic reaction proceeds through an unsymmetrical amphiphilic bis-allylpalladium intermediate. An introductory electrophilic attack on the terminal position of the unsubstituted allyl moiety is followed by a nucleophilic attack on the alkyl-substituted allyl ligand. A theoretical analysis was performed by applying density functional theory at the B3PW91/DZ+P level to study the substituent effects on the electrophilic attack. According to the theoretical results, the high regioselectivity can be ascribed to the electronic effects of the alkyl substituents: The terminal alkyl groups destabilize the η13-bis-allylpalladium intermediate of the reaction; in addition, the alkyl substitution increases the activation barrier for the electrophilic attack.

Ort, förlag, år, upplaga, sidor
2001. Vol. 66, nr 5, s. 1686-1693
Identifikatorer
URN: urn:nbn:se:su:diva-22711DOI: 10.1021/jo001374dOAI: oai:DiVA.org:su-22711DiVA, id: diva2:189304
Anmärkning
Part of urn:nbn:se:su:diva-105Tillgänglig från: 2004-04-22 Skapad: 2004-04-22 Senast uppdaterad: 2019-12-16Bibliografiskt granskad
Ingår i avhandling
1. Development of Palladium-Catalyzed Transformations Involving η1-Allypalladium Species
Öppna denna publikation i ny flik eller fönster >>Development of Palladium-Catalyzed Transformations Involving η1-Allypalladium Species
2004 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
Abstract [en]

This thesis is focused on investigation of the structure, reactivity and isomerization reactions of η1-allylpalladium complexes, which are key intermediates in catalytic transformations. The first part of this thesis concerns the structure and reactivity of bis-allylpalladium complexes. We have studied the regioselective palladium-catalyzed coupling reaction of various dialkylsubstituted allyl chlorides with allylstannanes and benzylidenemalonitrile, affording functionalized 1,7-octadienes. We have also found that benzylidenemalonitrile can be replaced by isocyanates providing bis-allylated amides. The second part is a computational study on the η3-η1-η3 isomerization of allylpalladium complexes. The mechanism of the isomerization was studied by DFT. It was found that the isomerization involves tetra-coordinated η1-allylpalladium intermediates. Alkyl substitution of the metalated carbon leads to destabilization of the η1-allylpalladium intermediate, which increases the activation energy of the isomerization process. The last part describes our efforts to extend the synthetic scope of mono-allylpalladium chemistry to include catalytic allylation of imine and aldehyde substrates. We have found that this reactivity can be achieved by the use of strongly coordinating tridentate ligands on palladium. The η1-allylpalladium intermediate has been observed by NMR-spectroscopy, and DFT calculations have been performed to show the feasibility of an electrophilic attack occuring on the allyl moiety.

Ort, förlag, år, upplaga, sidor
Stockholm: Institutionen för organisk kemi, 2004. s. 65
Nyckelord
Palladium, Homogenous catalysis, Allylation, Electrophilic substitution, Density functional calculations
Nationell ämneskategori
Organisk kemi
Identifikatorer
urn:nbn:se:su:diva-105 (URN)91-7265-868-1 (ISBN)
Disputation
2004-05-14, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 10:00 (Engelska)
Opponent
Handledare
Tillgänglig från: 2004-04-22 Skapad: 2004-04-22 Senast uppdaterad: 2010-02-11Bibliografiskt granskad

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