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Transition metal-catalysed isomerisation of allylic alcohols: Applications to C−C, C−F and C−Cl bond formation
Stockholm University, Faculty of Science, Department of Organic Chemistry. (Assoc. Prof. Belén Martín-Matute)
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
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.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University , 2013. , 73 p.
Keyword [en]
transiton metal-catalysis, allylic alcohols, isomerisation, halogenation
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-86758ISBN: 978-91-7447-627-9 (print)OAI: oai:DiVA.org:su-86758DiVA: diva2:589288
Public defence
2013-02-20, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 5: Manuscript.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

 

Available from: 2013-01-29 Created: 2013-01-17 Last updated: 2013-01-25Bibliographically approved
List of papers
1. Rhodium-catalysed isomerisation of allylic alcohols in water at ambient temperature
Open this publication in new window or tab >>Rhodium-catalysed isomerisation of allylic alcohols in water at ambient temperature
2010 (English)In: Green Chemistry, ISSN 1463-9262, E-ISSN 1463-9270, Vol. 12, no 9, 1628-1633 p.Article in journal (Refereed) 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.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-49442 (URN)10.1039/c004964f (DOI)000281613900019 ()
Note

authorCount :3

Available from: 2010-12-17 Created: 2010-12-14 Last updated: 2013-01-18Bibliographically approved
2. Rhodium-catalysed coupling of allylic, homoallylic, and bishomoallylic alcohols with aldehydes and N-tosylimines: insights into the mechanism
Open this publication in new window or tab >>Rhodium-catalysed coupling of allylic, homoallylic, and bishomoallylic alcohols with aldehydes and N-tosylimines: insights into the mechanism
2009 (English)In: Advanced Synthesis and Catalysis, ISSN 1615-4150, E-ISSN 1615-4169, Vol. 351, no 16, 2657-2666 p.Article in journal (Refereed) 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.

Keyword
aldehydes, allylic alcohols, isomerization, rhodium, N-tosylmines
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-42169 (URN)10.1002/adsc.200900448 (DOI)000272252900022 ()
Available from: 2010-08-18 Created: 2010-08-18 Last updated: 2013-01-18Bibliographically approved
3. Ir-catalysed formation of C-F bonds. From allylic alcohols to α-fluoroketones
Open this publication in new window or tab >>Ir-catalysed formation of C-F bonds. From allylic alcohols to α-fluoroketones
2011 (English)In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 47, no 29, 8331-8333 p.Article in journal (Refereed) 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.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-66618 (URN)10.1039/c1cc12653a (DOI)000292980900039 ()
Funder
Swedish Research CouncilInternational Interdisciplinary Materials Science Laboratory for Advanced Functional Materials
Note

authorCount :2

Available from: 2011-12-21 Created: 2011-12-20 Last updated: 2017-12-08Bibliographically approved
4. A facile synthesis of α-fluoro ketones catalyzed by [Cp*IrCl2](2)
Open this publication in new window or tab >>A facile synthesis of α-fluoro ketones catalyzed by [Cp*IrCl2](2)
2011 (English)In: Synthesis (Stuttgart), ISSN 0039-7881, E-ISSN 1437-210X, no 16, 2600-2608 p.Article in journal (Refereed) 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.

Keyword
iridium, fluorine, isomerization, alcohols, fluoro ketones
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-69249 (URN)10.1055/s-0030-1260130 (DOI)000293575500011 ()
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Note

authorCount :4

Available from: 2012-01-12 Created: 2012-01-11 Last updated: 2017-12-08Bibliographically approved
5. Synthesis of α-chlorinated ketones and aldehydes: Iridium-catalyzed tandem 1,3-H shift/chlorination of allylic alcohols
Open this publication in new window or tab >>Synthesis of α-chlorinated ketones and aldehydes: Iridium-catalyzed tandem 1,3-H shift/chlorination of allylic alcohols
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-87007 (URN)
Available from: 2013-01-24 Created: 2013-01-24 Last updated: 2013-01-25Bibliographically approved
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
Open this publication in new window or tab >>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
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-87009 (URN)
Available from: 2013-01-24 Created: 2013-01-24 Last updated: 2013-01-25Bibliographically approved

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