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Palladium-catalyzed Tandem Bis-allylation of Isocyanates
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 (engelsk)Inngår i: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 3, nr 6, s. 909-912Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

A tandem bis-allylation of p-toluenesulfonyl isocyanate can be achieved by palladium-catalyzed three-component coupling reaction with allylstannanes and allyl chlorides. A high level of regioselectivity can be obtained by the appropriate choice of the allylic substituents. The reaction mechanism and the regiochemistry of the reaction can be explained by formation of an amphoteric bis-allylpalladium intermediate. This bis-allylpalladium intermediate undergoes an initial electrophilic attack on one of the allyl moieties followed by a nucleophilic attack on the other.

sted, utgiver, år, opplag, sider
2001. Vol. 3, nr 6, s. 909-912
Identifikatorer
URN: urn:nbn:se:su:diva-22712DOI: 10.1021/ol015545sOAI: oai:DiVA.org:su-22712DiVA, id: diva2:189305
Merknad
Part of urn:nbn:se:su:diva-105Tilgjengelig fra: 2004-04-22 Laget: 2004-04-22 Sist oppdatert: 2019-12-16bibliografisk kontrollert
Inngår i avhandling
1. Development of Palladium-Catalyzed Transformations Involving η1-Allypalladium Species
Åpne denne publikasjonen i ny fane eller vindu >>Development of Palladium-Catalyzed Transformations Involving η1-Allypalladium Species
2004 (engelsk)Doktoravhandling, med artikler (Annet vitenskapelig)
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.

sted, utgiver, år, opplag, sider
Stockholm: Institutionen för organisk kemi, 2004. s. 65
Emneord
Palladium, Homogenous catalysis, Allylation, Electrophilic substitution, Density functional calculations
HSV kategori
Identifikatorer
urn:nbn:se:su:diva-105 (URN)91-7265-868-1 (ISBN)
Disputas
2004-05-14, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 10:00 (engelsk)
Opponent
Veileder
Tilgjengelig fra: 2004-04-22 Laget: 2004-04-22 Sist oppdatert: 2010-02-11bibliografisk kontrollert

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