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Room Temperature, Metal-Free Arylation of Aliphatic Alcohols
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.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2014 (English)In: ChemistryOpen, ISSN 2191-1363, Vol. 3, no 2, 54-57 p.Article in journal (Refereed) Published
Abstract [en]

Diaryliodonium salts are demonstrated as efficient arylating agents of aliphatic alcohols under metal-free conditions. The reaction proceeds at room temperature within 90min to give alkyl aryl ethers in good to excellent yields. Aryl groups with electron-withdrawing substituents are transferred most efficiently, and unsymmetric iodonium salts give chemoselective arylations. The methodology has been applied to the formal synthesis of butoxycaine.

Place, publisher, year, edition, pages
2014. Vol. 3, no 2, 54-57 p.
Keyword [en]
aliphatic alcohols, alkyl aryl ethers, arylation, diaryliodonium salts, hypervalent iodine
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-103962DOI: 10.1002/open.201402006ISI: 000334680800002OAI: oai:DiVA.org:su-103962DiVA: diva2:722868
Funder
Swedish Research Council, 621-2011-3608Wenner-Gren Foundations
Note

AuthorCount:4;

Available from: 2014-06-09 Created: 2014-05-27 Last updated: 2017-12-05Bibliographically approved
In thesis
1. Metal-Free O- and C-Arylation with Diaryliodonium Salts
Open this publication in new window or tab >>Metal-Free O- and C-Arylation with Diaryliodonium Salts
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis concerns the development of metal-free applications using diaryliodonium salts. The first project describes an arylation protocol of allylic and benzylic alcohols in aqueous media. The method proceeds under mild conditions and the ether products were obtained in moderate to good yields. The methodology was also expanded to include arylation of phenols, giving diaryl ethers in good to excellent yields. In the second project, an arylation method that included a wider range of aliphatic alcohols was developed. The scope of accessible alkyl aryl ethers was studied and included a comparative study of phenylation and nitrophenylation of various alcohols. Finally, a formal metal-free synthesis of butoxycain was performed, illustrating the applicability of the developed method.

The third project focused on the limitations and side reactions occurring in Chapter 2 and 3. First, an approach to access symmetric diaryl ethers via arylation of hydroxide was presented. This reaction gave rise to a number of side products, which we hypothesized to originate from aryne-type intermediates. A mechanism for the formation of these side products was suggested, supported by trapping and deuterium labeling experiments.

Oxidation of the alcohol to the corresponding ketone was also observed and the mechanism of this interesting side reaction was investigated. The latter was suggested to proceed via an intramolecular oxidation without the involvement of radicals or arynes.

The fourth project covers a method to synthesize highly sterically congested alkyl aryl ethers via arylation of tertiary alcohols using diaryliodonium salts. The method displayed a broad scope of tertiary alcohols and was also suitable for fluorinated alcohols.

The final project detailed in this thesis deals with C-arylation with diaryliodonium salts, showcasing nitroalkanes as well as a nitro ester as suitable nucleophiles for metal-free arylation. 

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2017. 85 p.
Keyword
Hypervalent Iodine, Alkyl Aryl Ethers, Nitro Compounds, Alcohols, Diaryliodonium Salts
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-140944 (URN)978-91-7649-702-9 (ISBN)978-91-7649-703-6 (ISBN)
Public defence
2017-05-12, Magnélisalen, Kemiska Övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 3: Manuscript.

Available from: 2017-04-19 Created: 2017-03-24 Last updated: 2017-04-11Bibliographically approved

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