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Rhodium-catalysed coupling of allylic, homoallylic, and bishomoallylic alcohols with aldehydes and N-tosylimines: insights into the mechanism
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.
2009 (Engelska)Ingår i: Advanced Synthesis and Catalysis, ISSN 1615-4150, E-ISSN 1615-4169, Vol. 351, nr 16, s. 2657-2666Artikel i tidskrift (Refereegranskat) Published
Abstract [en]

The isomerisation of alkenols followed by reaction with aldehydes or N-tosylimines catalysed by rhodium complexes has been studied. The catalytically active rhodium complex is formed in situ from commercially available (cyclooctadiene)rhodium(l) chloride dimer [Rh(COD)Cl](2). The tandem process affords aldol and Mannich-type products in excellent yields. The key to the success of the coupling reaction is the activation of the catalysts by reaction with postassium tert-butoxide (t-BuOK), which promotes a catalytic cycle via alkoxides rather than rhodium hydrides. This mechanism minimises the formation of unwanted by-products. The mechanism has been studied by (1)H NMR spectroscopy and deuterium labelling experiments.

Ort, förlag, år, upplaga, sidor
2009. Vol. 351, nr 16, s. 2657-2666
Nyckelord [en]
aldehydes, allylic alcohols, isomerization, rhodium, N-tosylmines
Nationell ämneskategori
Organisk kemi
Forskningsämne
organisk kemi
Identifikatorer
URN: urn:nbn:se:su:diva-42169DOI: 10.1002/adsc.200900448ISI: 000272252900022OAI: oai:DiVA.org:su-42169DiVA, id: diva2:344238
Tillgänglig från: 2010-08-18 Skapad: 2010-08-18 Senast uppdaterad: 2017-12-12Bibliografiskt granskad
Ingår i avhandling
1. Transition metal-catalysed isomerisation of allylic alcohols: Applications to C−C, C−F and C−Cl bond formation
Öppna denna publikation i ny flik eller fönster >>Transition metal-catalysed isomerisation of allylic alcohols: Applications to C−C, C−F and C−Cl bond formation
2013 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
Abstract [en]

The focus of this thesis has been to develop selective and atom-economical methods for carbon-carbon and carbon-heteroatom bond formation, and to some extent improve on existing findings in this area. More specifically, methods for the catalytic generation of enolates from allylic alcohols and their in situ functionalisation with electrophilic reagents are described.  

In the first part of this thesis, a method for the Rh-catalysed redox-isomerisation of allylic alcohols into carbonyl compounds under environmentally benign conditions is described. The reaction takes place at room temperature, in the absence of acids or bases, using water as the only solvent, and it is applicable to both primary and secondary allylic alcohols.

The second part describes the combination of an isomerisation reaction of allylic alcohols with a C−C bond formation, catalysed by a rhodium complex. In this way, allylic alcohols were coupled with aldehydes and N-tosylimines to give aldol and Mannich-type products. In addition to allylic alcohols, homoallylic and bishomoallylic alcohols could be used as enolate precursors, and this is the first report where the latter two substrate types have been used in such a reaction.       

In the remaining parts of the thesis, an iridium-catalysed isomerisation of allylic alcohols has been combined with an electrophilic halogenation step to provide a conceptually new method for the synthesis of α-halogenated carbonyl compounds. In this way, α-fluoro and α-chloroketones have been synthesised as single constitutional isomers, with the regiochemistry of the final products determined by the position of the double bond in the allylic alcohols. The reactions are tolerant to air, run in water-organic solvent mixtures, and proceed at room temperature.

Ort, förlag, år, upplaga, sidor
Stockholm: Department of Organic Chemistry, Stockholm University, 2013. s. 73
Nyckelord
transiton metal-catalysis, allylic alcohols, isomerisation, halogenation
Nationell ämneskategori
Organisk kemi
Forskningsämne
organisk kemi
Identifikatorer
urn:nbn:se:su:diva-86758 (URN)978-91-7447-627-9 (ISBN)
Disputation
2013-02-20, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (Engelska)
Opponent
Handledare
Anmärkning

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 5: Manuscript. Paper 6: Manuscript.

 

Tillgänglig från: 2013-01-29 Skapad: 2013-01-17 Senast uppdaterad: 2013-01-25Bibliografiskt granskad

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Ahlsten, NannaMartín-Matute, Belén
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