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Synthesis of α-chlorinated ketones and aldehydes: Iridium-catalyzed tandem 1,3-H shift/chlorination of allylic alcohols
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi. (Assoc. Prof. Belén Martín-Matute)
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi. (Assoc. Prof. Bélen Martín-Matute)
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.
(engelsk)Manuskript (preprint) (Annet vitenskapelig)
HSV kategori
Forskningsprogram
organisk kemi
Identifikatorer
URN: urn:nbn:se:su:diva-87007OAI: oai:DiVA.org:su-87007DiVA, id: diva2:600518
Tilgjengelig fra: 2013-01-24 Laget: 2013-01-24 Sist oppdatert: 2013-01-25bibliografisk kontrollert
Inngår i avhandling
1. Transition metal-catalysed isomerisation of allylic alcohols: Applications to C−C, C−F and C−Cl bond formation
Åpne denne publikasjonen i ny fane eller vindu >>Transition metal-catalysed isomerisation of allylic alcohols: Applications to C−C, C−F and C−Cl bond formation
2013 (engelsk)Doktoravhandling, med artikler (Annet vitenskapelig)
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.

sted, utgiver, år, opplag, sider
Stockholm: Department of Organic Chemistry, Stockholm University, 2013. s. 73
Emneord
transiton metal-catalysis, allylic alcohols, isomerisation, halogenation
HSV kategori
Forskningsprogram
organisk kemi
Identifikatorer
urn:nbn:se:su:diva-86758 (URN)978-91-7447-627-9 (ISBN)
Disputas
2013-02-20, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (engelsk)
Opponent
Veileder
Merknad

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 5: Manuscript.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

 

Tilgjengelig fra: 2013-01-29 Laget: 2013-01-17 Sist oppdatert: 2013-01-25bibliografisk kontrollert

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