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Metal-Free Arylation of Oxygen Nucleophiles with Diaryliodonium Salts
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2012 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 18, no 44, 14140-14149 p.Article in journal (Refereed) Published
Abstract [en]

Phenols and carboxylic acids are efficiently arylated with diaryliodonium salts. The reaction conditions are mild, metal free, and avoid the use of halogenated solvents, additives, and excess reagents. The products are obtained in good-to-excellent yields after short reaction times. Steric hindrance is very well tolerated, both in the nucleophile and diaryliodonium salt. The scope includes ortho-and halo-substituted products, which are difficult to obtain by metal-catalyzed protocols. Many functional groups are tolerated, including carbonyl groups, heteroatoms, and alkenes. Unsymmetric salts can be chemoselectively utilized to obtain products with hitherto unreported levels of steric congestion. The arylation has been extended to sulfonic acids, which can be converted to sulfonate esters by two different approaches. With recent advances in efficient synthetic procedures for diaryliodonium salts the reagents are now inexpensive and readily available. The iodoarene byproduct formed from the iodonium reagent can be recovered quantitatively and used to regenerate the diaryliodonium salt, which improves the atom economy.

Place, publisher, year, edition, pages
2012. Vol. 18, no 44, 14140-14149 p.
Keyword [en]
aryl esters, arylation, diaryl ethers, hypervalent iodine, synthetic methods
National Category
Chemical Sciences Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-82958DOI: 10.1002/chem.201201645ISI: 000310473900031OAI: oai:DiVA.org:su-82958DiVA: diva2:576860
Funder
Swedish Research Council, 621-2008-3709Carl Tryggers foundation , 08:288Carl Tryggers foundation , 09:281
Note

AuthorCount:3;

Available from: 2012-12-14 Created: 2012-12-03 Last updated: 2017-12-06Bibliographically approved
In thesis
1. Development and Applications of Hypervalent Iodine Compounds: Powerful Arylation and Oxidation Reagents
Open this publication in new window or tab >>Development and Applications of Hypervalent Iodine Compounds: Powerful Arylation and Oxidation Reagents
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The first part of this thesis describes the efficient synthesis of several hypervalent iodine(III) compounds. Electron-rich diaryliodonium salts have been synthesized in a one-pot procedure, employing mCPBA as the oxidant. Both symmetric and unsymmetric diaryliodonium tosylates can be isolated in high yields. An in situ anion exchange also enables the synthesis of previously unobtainable diaryliodonium triflates.

A large-scale protocol for the synthesis of a derivative of Koser’s reagent, that is an isolable intermediate in the diaryliodonium tosylate synthesis, is furthermore described. The large-scale synthesis is performed in neat TFE, which can be recovered and recycled. This is very desirable from an environmental point of view.

One of the few described syntheses of enantiopure diaryliodonium salts is discussed. Three different enantiopure diaryliodonium salts bearing electron-rich substituents are synthesized in moderate to high yields. The synthesis of these three salts shows the challenge in the preparation of electron-rich substituted unsymmetric salts.

The second part of the thesis describes the application of both symmetric and unsymmetric diaryliodonium salts in organic synthesis. A metal-free efficient and fast method for the synthesis of diaryl ethers from diaryliodonium salts has been developed. The substrate scope is wide as both the phenol and the diaryliodonium salt can be varied. Products such as halogenated ethers, ortho-substituted ethers and bulky ethers, that are difficult to obtain with metal-catalyzed procedures, are readily prepared. The mild protocol allows arylation of racemization-prone a-amino acid derivatives without loss of enantiomeric excess.

A chemoselectivity investigation was conducted, in which unsymmetric diaryliodonium salts were employed in the arylation of three different nucleophiles in order to understand the different factors that influence which aryl moiety that is transferred to the nucleophile.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2012. 71 p.
Keyword
hypervalent iodine compounds, diaryliodonium salts, oxidation, Koser's reagent, arylation, phenols, diaryl ethers, chemoselectivity
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-75810 (URN)978-91-7447-505-0 (ISBN)
Public defence
2012-06-05, 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 2: Accepted. Paper 5: Submitted. Paper 6: Manuscript.

Available from: 2012-05-10 Created: 2012-04-27 Last updated: 2013-08-09Bibliographically approved

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