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Palladium-Catalyzed Nucleophilic Substitution of Alcohols: Mechanistic Studies and Synthetic Applications
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Synthetical Organic Chemistry.
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
Keyword [en]
palladium, nucleophilic substitution, mechanism
National Category
Organic Chemistry
Research subject
Organic Chemistry
URN: urn:nbn:se:uu:diva-209541ISBN: 978-91-554-8785-0OAI: diva2:658388
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
List of papers
1. Pd-Catalyzed Transfer Hydrogenolysis of Primary, Secondary, and Tertiary Benzylic Alcohols by Formic Acid: A Mechanistic Study
Open this publication in new window or tab >>Pd-Catalyzed Transfer Hydrogenolysis of Primary, Secondary, and Tertiary Benzylic Alcohols by Formic Acid: A Mechanistic Study
2013 (English)In: ACS Catalysis, ISSN 2155-5435, Vol. 3, no 4, 635-642 p.Article in journal (Refereed) Published
Abstract [en]

A palladium-catalyzed transfer hydrogenolysis of primary, secondary, and tertiary benzylic alcohols by formic acid has been developed and studied. The product hydrocarbons were obtained in excellent yields from bothsecondary and tertiary benzylic alcohols and in good yields for primary benzylicalcohols. The rate of disappearance of 1-phenylethanol (1) follows zero-order dependence in 1 and first-order dependence in formic acid and palladium. Catalytic amounts of base inhibit a competing disproportionation reaction ofalcohol to alkane and ketone, and an optimum was obtained when 5 equiv ofbase to palladium was used Deuterium kinetic isotope studies for the transferhydrogenolysis reveal individual isotope effects for the hydridic position (k(CHOH)/k(CDOH) = 2.26 +/- 0.24) and the protic position (k(CHOH)/k(CHOD) = 0.62 +/- 0.06) of the formic acid. Simultaneous deuteration in both positions offormic acid gave a combined isotope effect of (k(CHOH)/k(CDOD) = 1.41 +/- 0.11). We propose a mechanism involving the following steps: a competitive inhibition of the open palladium site by adsorption of the formate anion to generate formato-palladium species, followed by a reversible protonation and arate-limiting hydride transfer to obtain the active palladium with chemisorbed hydrogen that performs the hydrogenolysis of the alcohol in a fast reaction step.

National Category
Natural Sciences
urn:nbn:se:uu:diva-196658 (URN)10.1021/cs300785r (DOI)000317328000024 ()
The Swedish Energy Agency
Available from: 2013-03-12 Created: 2013-03-12 Last updated: 2014-01-23Bibliographically approved
2. An atom efficient route to N-aryl and N-alkyl pyrrolines by transition metal catalysis
Open this publication in new window or tab >>An atom efficient route to N-aryl and N-alkyl pyrrolines by transition metal catalysis
2011 (English)In: Organic and biomolecular chemistry, ISSN 1477-0520, E-ISSN 1477-0539, Vol. 9, no 7, 2548-2554 p.Article in journal (Refereed) Published
Abstract [en]

The synthesis of N-aryl, N-tosyl, and N-alkyl pyrrolines from allyl alcohols and amines has been developed. The reaction sequence includes a palladium-catalyzed allylation step in which non-manipulated allyl alcohol is used to generate the diallylated amine in good to excellent yield. An excess of allyl alcohol was necessary for efficient diallylation of the amine, where the excess alcohol could be recycled three times. For aryl and tosyl amines, Pd[P(OPh)(3)](4) was used and for benzyl and alkyl amines a catalytic system comprising Pd(OAc)(2), (PBu3)-Bu-n, and BEt3 was used. Both the electronic properties and the steric influence of the amine affected the efficiency of the allylation. The isolated diallylated amines were transformed into their corresponding pyrrolines by ring-closing metathesis catalyzed by (H(2)IMes)(PCy3)Cl2RuCHPh in good to excellent yield. A one-pot reaction was developed in which aniline was transformed into the corresponding pyrroline without isolating the diallylated intermediate. This one-pot reaction was successfully scaled-up to 1 mL of aniline in which the N-phenyl pyrroline was isolated in 95% yield. The versatility of the reaction in which 3-methyl-1-phenyl pyrroline was prepared in two-steps was demonstrated.

National Category
Biochemistry and Molecular Biology
urn:nbn:se:uu:diva-150726 (URN)10.1039/c0ob00383b (DOI)000288456700063 ()21344095 (PubMedID)
Available from: 2011-04-05 Created: 2011-04-05 Last updated: 2014-01-23Bibliographically approved
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4. Equilibrium Study of Pd(dba)2 and P(OPh)3 in the Pd-Catalyzed Allylation of Aniline by Allyl Alcohol
Open this publication in new window or tab >>Equilibrium Study of Pd(dba)2 and P(OPh)3 in the Pd-Catalyzed Allylation of Aniline by Allyl Alcohol
Show others...
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.

National Category
Natural Sciences
urn:nbn:se:uu:diva-218947 (URN)10.1021/om4009873 (DOI)000329879900029 ()
Available from: 2014-02-27 Created: 2014-02-20 Last updated: 2014-09-11Bibliographically approved

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