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Iodonium Salts: Preparation, Chemoselectivity and Metal-Catalyzed Applications
Stockholm University, Faculty of Science, Department of Organic Chemistry.ORCID iD: 0000-0002-9999-5137
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis concerns the preparation and use of diaryliodonium salts. In Project I various unsymmetrical diaryliodonium salts were reacted with three different nucleophiles in order to study the chemoselectivity of the reactions of the salts. The main focus of this project was to gain a deeper understanding of the underlying factors that affect the chemoselectivity in transition metal-free arylation reactions. They were found to be very nucleophile-dependent. Some nucleophiles were very sensitive to electronic effects, whereas others were sensitive to steric factors. Ultimately, some arenes are never transferred. A very interesting scrambling reaction was also observed under the reaction conditions, where unsymmetrical diaryliodonium salts form symmetrical salts in situ.

Project II details the preparation of N-heteroaryliodonium salts via a one-pot procedure. The salts were designed so that the N-heteroaryl moiety was selectively transferred in applications both with and without transition metals. The chemoselectivity was demonstrated by selective transfer of the pyridyl group onto two different nucleophiles.

The third project in the thesis discusses the synthesis of alkynyl(aryl)iodonium salts and alkynylbenziodoxolones from arylsilanes. This protocol could potentially be a very useful complement to the existing procedures, in which boronic acids are used.

The last part of the thesis (Project IV) describes a C-2 selective arylation of indoles where diaryliodonium salts were used in combination with hetero-geneous palladium catalysis. This transformation was performed in water at ambient temperature to 50 °C, and tolerated variations of both the indole and the diaryliodonium salt. Importantly, several N-H indoles could be arylated. The MCF-supported Pd-catalyst showed very little leaching and it was demonstrated that the main part of the reaction occurred via heterogeneous catalysis.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University , 2014. , p. 75
Keywords [en]
Diaryliodonium salts, chemoselectivity, heterogeneous catalysis
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-107694ISBN: 978-91-7447-999-7 (print)OAI: oai:DiVA.org:su-107694DiVA, id: diva2:749581
Public defence
2014-10-24, 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 3: Manuscript. Paper 4: Accepted.

Available from: 2014-10-02 Created: 2014-09-24 Last updated: 2014-11-18Bibliographically approved
List of papers
1. Arylation with Unsymmetrical Diaryliodonium Salts: A Chemoselectivity Study
Open this publication in new window or tab >>Arylation with Unsymmetrical Diaryliodonium Salts: A Chemoselectivity Study
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2013 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 19, no 31, p. 10334-10342Article in journal (Refereed) Published
Abstract [en]

Phenols, anilines, and malonates have been arylated under metal-free conditions with twelve aryl(phenyl)iodonium salts in a systematic chemoselectivity study. A new “anti-ortho effect” has been identified in the arylation of malonates. Several “dummy groups” have been found that give complete chemoselectivity in the transfer of the phenyl moiety, irrespective of the nucleophile. An aryl exchange in the diaryliodonium salts has been observed under certain arylation conditions. DFT calculations have been performed to investigate the reaction mechanism and to elucidate the origins of the observed selectivities. These results are expected to facilitate the design of chiral diaryliodonium salts and the development of catalytic arylation reactions that are based on these sustainable and metal-free reagents.

Keywords
arylation, chemoselectivity, DFT calculations, hypervalent compounds, ligand exchange
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-75778 (URN)10.1002/chem.201300860 (DOI)000321983700034 ()
Funder
Swedish Research Council, 621-2011-3608
Available from: 2012-04-26 Created: 2012-04-26 Last updated: 2017-12-07Bibliographically approved
2. One-Pot Synthesis and Applications of N-Heteroaryl Iodonium Salts
Open this publication in new window or tab >>One-Pot Synthesis and Applications of N-Heteroaryl Iodonium Salts
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2014 (English)In: ChemistryOpen, ISSN 2191-1363, Vol. 3, no 1, p. 19-22Article in journal (Refereed) Published
Abstract [en]

An efficient one-pot synthesis of N-heteroaryl iodonium triflates from the corresponding N-heteroaryl iodide and arene has been developed. The reaction conditions resemble our previous one-pot syntheses, with suitable modifications to allow N-heteroaryl groups. The reaction time is only 30min, and no anion exchange is required. The obtained iodonium salts were isolated in a protonated form, these salts can either be employed directly in applications or be deprotonated prior to use. The aryl groups were chosen to induce chemoselective transfer of the heteroaryl moiety to various nucleophiles. The reactivity and chemoselectivity of these iodonium salts were demonstrated by selectively introducing a pyridyl moiety onto both oxygen and carbon nucleophiles in good yields.

Keywords
arylation, heterocycles, hypervalent iodine, iodonium salts, oxidation
National Category
Chemical Sciences
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-105258 (URN)10.1002/open.201300042 (DOI)000333393700003 ()
Funder
Swedish Research Council, 621-2011-3608
Note

AuthorCount:5;

Available from: 2014-06-25 Created: 2014-06-24 Last updated: 2017-12-05Bibliographically approved
3. Synthesis of Alkynyl(aryl)iodonium salts from TMS-alkynes
Open this publication in new window or tab >>Synthesis of Alkynyl(aryl)iodonium salts from TMS-alkynes
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-107699 (URN)
Available from: 2014-09-24 Created: 2014-09-24 Last updated: 2014-09-25
4. C-2 Selective Arylation of Indoles with Heterogeneous Nanopalladium and Diaryliodonium Salts
Open this publication in new window or tab >>C-2 Selective Arylation of Indoles with Heterogeneous Nanopalladium and Diaryliodonium Salts