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Equilibrium Study of Pd(dba)2 and P(OPh)3 in the Pd-Catalyzed Allylation of Aniline by Allyl Alcohol
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC. (Organisk synteskemi)
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Inorganic Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Analytical Chemistry.
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2014 (English)In: Organometallics, ISSN 0276-7333, E-ISSN 1520-6041, Vol. 33, no 1, 249-253 p.Article in journal (Refereed) Published
Abstract [en]

Reaction of Pd(dba)2 and P(OPh)3 shows a unique equilibrium where the Pd[P(OPh)3]3 complex is favored over both Pd(dba)[P(OPh)3]2 and Pd[P(OPh)3]4 complexes at room temperature. At a lower temperature, Pd[P(OPh)3]4 becomes the most abundant complex in solution. X-ray studies of Pd[P(OPh)3]3 and Pd(dba)[P(OPh)3]2 complexes show that both complexes have a trigonal geometry with a Pd–P distance of 2.25 Å due to the π-acidity of the phosphite ligand. In solution, pure Pd(dba)[P(OPh)3]2 complex equilibrates to the favored Pd[P(OPh)3]3 complex, which is the most stable complex of those studied, and also forms the most active catalytic species. This catalyst precursor dissociates one ligand to give the reactive Pd[P(OPh)3]2, which performs an oxidative addition of nonmanipulated allyl alcohol to generate the π-allyl-Pd[P(OPh)3]2 intermediate according to ESI-MS studies.

Place, publisher, year, edition, pages
2014. Vol. 33, no 1, 249-253 p.
National Category
Natural Sciences
URN: urn:nbn:se:uu:diva-218947DOI: 10.1021/om4009873ISI: 000329879900029OAI: oai:DiVA.org:uu-218947DiVA: diva2:699325
Available from: 2014-02-27 Created: 2014-02-20 Last updated: 2014-09-11Bibliographically approved
In thesis
1. Palladium-Catalyzed Nucleophilic Substitution of Alcohols: Mechanistic Studies and Synthetic Applications
Open this publication in new window or tab >>Palladium-Catalyzed Nucleophilic Substitution of Alcohols: Mechanistic Studies and Synthetic Applications
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis deals with the palladium-catalyzed nucleophilic substitution of π-activated alcohols in which the C–O bond of a non-manipulated hydroxyl group is cleaved. The thesis is divided in two chapters describing two different catalytic systems.

Chapter 2 describes a heterogeneous palladium-catalyzed transfer hydrogenolysis of primary, secondary, and tertiary benzylic alcohols to generate the corresponding aromatic hydrocarbons using formic acid as the hydrogen donor. A detailed mechanistic investigation of this reaction has been conducted that establish the kinetic order of each reaction component and also the deuterium kinetic isotope effects. This data provide a mechanistic picture that the hydride transfer from formic acid to palladium, and not the C–O bond cleavage, is involved in the rate-determining step and that a catalytic amount of a base promotes the transfer hydrogenolysis.

Chapter 3 describes the development, mechanistic studies and synthetic scope of a homogeneous palladium-catalyzed amination of allylic alcohols. Isolation of the catalyst precursor and equilibrium studies of the palladium and π-acidic triphenylphosphite ligand show unique properties of this catalytic system. Stereochemical, kinetic, and kinetic isotope studies have been performed to provide insight into the mechanism of C–O bond cleavage of allylic alcohol and C–N bond formation catalyzed by the palladium complex. Interestingly, both O–H and C–O bond cleavages are involved in rate-determining steps.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2013. 63 p.
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1092
palladium, nucleophilic substitution, mechanism
National Category
Organic Chemistry
Research subject
Organic Chemistry
urn:nbn:se:uu:diva-209541 (URN)978-91-554-8785-0 (ISBN)
Public defence
2013-12-09, B21, Husargatan 3, Uppsala, 10:15 (English)
Available from: 2013-11-18 Created: 2013-10-21 Last updated: 2014-09-11

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Sawadjoon, SupapornOrthaber, AndreasSjöberg, Per J. R.Samec, Joseph S. M.
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