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An atom efficient route to N-aryl and N-alkyl pyrrolines by transition metal catalysis
Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för biokemi och organisk kemi, Organisk kemi.
Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för biokemi och organisk kemi, Organisk kemi.
2011 (Engelska)Ingår i: Organic and biomolecular chemistry, ISSN 1477-0520, E-ISSN 1477-0539, Vol. 9, nr 7, s. 2548-2554Artikel i tidskrift (Refereegranskat) 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.

Ort, förlag, år, upplaga, sidor
2011. Vol. 9, nr 7, s. 2548-2554
Nationell ämneskategori
Biokemi och molekylärbiologi
Identifikatorer
URN: urn:nbn:se:uu:diva-150726DOI: 10.1039/c0ob00383bISI: 000288456700063PubMedID: 21344095OAI: oai:DiVA.org:uu-150726DiVA, id: diva2:408541
Tillgänglig från: 2011-04-05 Skapad: 2011-04-05 Senast uppdaterad: 2017-12-11Bibliografiskt granskad
Ingår i avhandling
1. Palladium-Catalyzed Nucleophilic Substitution of Alcohols: Mechanistic Studies and Synthetic Applications
Öppna denna publikation i ny flik eller fönster >>Palladium-Catalyzed Nucleophilic Substitution of Alcohols: Mechanistic Studies and Synthetic Applications
2013 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
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.

Ort, förlag, år, upplaga, sidor
Uppsala: Acta Universitatis Upsaliensis, 2013. s. 63
Serie
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1092
Nyckelord
palladium, nucleophilic substitution, mechanism
Nationell ämneskategori
Organisk kemi
Forskningsämne
Organisk kemi
Identifikatorer
urn:nbn:se:uu:diva-209541 (URN)978-91-554-8785-0 (ISBN)
Disputation
2013-12-09, B21, Husargatan 3, Uppsala, 10:15 (Engelska)
Opponent
Handledare
Tillgänglig från: 2013-11-18 Skapad: 2013-10-21 Senast uppdaterad: 2014-09-11

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