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Transition metal-catalysed isomerisation of allylic alcohols: Applications to C−C, C−F and C−Cl bond formation
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi. (Assoc. Prof. Belén Martín-Matute)
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 [en]
transiton metal-catalysis, allylic alcohols, isomerisation, halogenation
Nationell ämneskategori
Organisk kemi
Forskningsämne
organisk kemi
Identifikatorer
URN: urn:nbn:se:su:diva-86758ISBN: 978-91-7447-627-9 (tryckt)OAI: oai:DiVA.org:su-86758DiVA, id: diva2:589288
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
Delarbeten
1. Rhodium-catalysed isomerisation of allylic alcohols in water at ambient temperature
Öppna denna publikation i ny flik eller fönster >>Rhodium-catalysed isomerisation of allylic alcohols in water at ambient temperature
2010 (Engelska)Ingår i: Green Chemistry, ISSN 1463-9262, E-ISSN 1463-9270, Vol. 12, nr 9, s. 1628-1633Artikel i tidskrift (Refereegranskat) Published
Abstract [en]

An environmentally benign method for the transformation of allylic alcohols into carbonyl compounds is described. Using [Rh(COD(CH3CN)(2)]BF4 (2) in combination with 1,3,5-triaza-7-phosphaadamantane (PTA, 1) as the catalytic system in water results in a very fast redox isomerisation of a variety of secondary allylic alcohols at ambient temperature. Also, some primary allylic alcohols can be isomerised into the corresponding aldehydes. The active complex, which in some cases can be used in catalyst loadings as low as 0.5 mol%, is formed in situ from commercially available reagents. Based on deuterium labelling studies, a tentative mechanism involving metal-enone intermediates is presented.

Nationell ämneskategori
Organisk kemi
Forskningsämne
organisk kemi
Identifikatorer
urn:nbn:se:su:diva-49442 (URN)10.1039/c004964f (DOI)000281613900019 ()
Anmärkning

authorCount :3

Tillgänglig från: 2010-12-17 Skapad: 2010-12-14 Senast uppdaterad: 2017-12-11Bibliografiskt granskad
2. Rhodium-catalysed coupling of allylic, homoallylic, and bishomoallylic alcohols with aldehydes and N-tosylimines: insights into the mechanism
Öppna denna publikation i ny flik eller fönster >>Rhodium-catalysed coupling of allylic, homoallylic, and bishomoallylic alcohols with aldehydes and N-tosylimines: insights into the mechanism
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.

Nyckelord
aldehydes, allylic alcohols, isomerization, rhodium, N-tosylmines
Nationell ämneskategori
Organisk kemi
Forskningsämne
organisk kemi
Identifikatorer
urn:nbn:se:su:diva-42169 (URN)10.1002/adsc.200900448 (DOI)000272252900022 ()
Tillgänglig från: 2010-08-18 Skapad: 2010-08-18 Senast uppdaterad: 2017-12-12Bibliografiskt granskad
3. Ir-catalysed formation of C-F bonds. From allylic alcohols to α-fluoroketones
Öppna denna publikation i ny flik eller fönster >>Ir-catalysed formation of C-F bonds. From allylic alcohols to α-fluoroketones
2011 (Engelska)Ingår i: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 47, nr 29, s. 8331-8333Artikel i tidskrift (Refereegranskat) Published
Abstract [en]

A novel iridium-catalysed tandem isomerisation/C-F bond formation from allylic alcohols and Selectfluor® to prepare α-fluorinated ketones as single constitutional isomers is reported.

Nationell ämneskategori
Organisk kemi
Forskningsämne
organisk kemi
Identifikatorer
urn:nbn:se:su:diva-66618 (URN)10.1039/c1cc12653a (DOI)000292980900039 ()
Forskningsfinansiär
VetenskapsrådetInternational Interdisciplinary Materials Science Laboratory for Advanced Functional Materials
Anmärkning

authorCount :2

Tillgänglig från: 2011-12-21 Skapad: 2011-12-20 Senast uppdaterad: 2017-12-08Bibliografiskt granskad
4. A facile synthesis of α-fluoro ketones catalyzed by [Cp*IrCl2](2)
Öppna denna publikation i ny flik eller fönster >>A facile synthesis of α-fluoro ketones catalyzed by [Cp*IrCl2](2)
2011 (Engelska)Ingår i: Synthesis (Stuttgart), ISSN 0039-7881, E-ISSN 1437-210X, nr 16, s. 2600-2608Artikel i tidskrift (Refereegranskat) Published
Abstract [en]

Allylic alcohols are isomerized into enolates (enols) by [Cp*IrCl2]2. The enolates react with Selectfluor present in the reaction media. This method produces α-fluoro ketones as single constitutional isomers in high yields.

Nyckelord
iridium, fluorine, isomerization, alcohols, fluoro ketones
Nationell ämneskategori
Organisk kemi
Forskningsämne
organisk kemi
Identifikatorer
urn:nbn:se:su:diva-69249 (URN)10.1055/s-0030-1260130 (DOI)000293575500011 ()
Forskningsfinansiär
VetenskapsrådetKnut och Alice Wallenbergs Stiftelse
Anmärkning

authorCount :4

Tillgänglig från: 2012-01-12 Skapad: 2012-01-11 Senast uppdaterad: 2017-12-08Bibliografiskt granskad
5. Synthesis of α-chlorinated ketones and aldehydes: Iridium-catalyzed tandem 1,3-H shift/chlorination of allylic alcohols
Öppna denna publikation i ny flik eller fönster >>Synthesis of α-chlorinated ketones and aldehydes: Iridium-catalyzed tandem 1,3-H shift/chlorination of allylic alcohols
(Engelska)Manuskript (preprint) (Övrigt vetenskapligt)
Nationell ämneskategori
Organisk kemi
Forskningsämne
organisk kemi
Identifikatorer
urn:nbn:se:su:diva-87007 (URN)
Tillgänglig från: 2013-01-24 Skapad: 2013-01-24 Senast uppdaterad: 2013-01-25Bibliografiskt granskad
6. Synthesis of 4,5-disubstituted 2-amino-1,3-thiazoles from α,β-unsaturated ketones: Preparation of 5-Benzyl-4-methyl-1,3-thiazol-2-amine hydrochloride
Öppna denna publikation i ny flik eller fönster >>Synthesis of 4,5-disubstituted 2-amino-1,3-thiazoles from α,β-unsaturated ketones: Preparation of 5-Benzyl-4-methyl-1,3-thiazol-2-amine hydrochloride
(Engelska)Manuskript (preprint) (Övrigt vetenskapligt)
Nationell ämneskategori
Organisk kemi
Forskningsämne
organisk kemi
Identifikatorer
urn:nbn:se:su:diva-87009 (URN)
Tillgänglig från: 2013-01-24 Skapad: 2013-01-24 Senast uppdaterad: 2013-01-25Bibliografiskt granskad

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