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An atom efficient route to N-aryl and N-alkyl pyrrolines by transition metal catalysis
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Biochemistry and Organic Chemistry, Organic Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Biochemistry and Organic Chemistry, Organic Chemistry.
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.

Place, publisher, year, edition, pages
2011. Vol. 9, no 7, 2548-2554 p.
National Category
Biochemistry and Molecular Biology
Identifiers
URN: urn:nbn:se:uu:diva-150726DOI: 10.1039/c0ob00383bISI: 000288456700063PubMedID: 21344095OAI: oai:DiVA.org:uu-150726DiVA: diva2:408541
Available from: 2011-04-05 Created: 2011-04-05 Last updated: 2017-12-11Bibliographically 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.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1092
Keyword
palladium, nucleophilic substitution, mechanism
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
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)
Opponent
Supervisors
Available from: 2013-11-18 Created: 2013-10-21 Last updated: 2014-09-11

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Samec, Joseph S. M.

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