Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Metal-Free C-Arylation of Nitro Compounds 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. Wallenberg Research Centre at Stellenbosch University, South Africa.
2015 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 17, no 18, 4554-4557 p.Article in journal (Refereed) Published
Abstract [en]

An efficient, mild, and metal-free arylation of nitro-alkanes with diaryliodonium salts has been developed, giving easy access to tertiary nitro compounds. The reaction proceeds in high yields without the need for excess reagents and can be extended to alpha-arylation of nitroesters. Nitroalkanes were selectively C-arylated in the presence of other easily arylated functional groups, such as phenols and aliphatic alcohols.

Place, publisher, year, edition, pages
2015. Vol. 17, no 18, 4554-4557 p.
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-122329DOI: 10.1021/acs.orglett.5b02270ISI: 000361867800040OAI: oai:DiVA.org:su-122329DiVA: diva2:875283
Funder
Carl Tryggers foundation
Available from: 2015-12-01 Created: 2015-10-29 Last updated: 2017-04-03Bibliographically 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

Open Access in DiVA

fulltext(645 kB)40 downloads
File information
File name FULLTEXT01.pdfFile size 645 kBChecksum SHA-512
397b755b6de28ca4eae42fc7f9bb5abbbcdabf8c7fc107a07f2f66be84cc6520e63fec6791013d5c4b5410ddd403bb2811660b1e6ffe5ec75dc043b78a42320b
Type fulltextMimetype application/pdf

Other links

Publisher's full text

Search in DiVA

By author/editor
Dey, ChandanLindstedt, ErikOlofsson, Berit
By organisation
Department of Organic Chemistry
In the same journal
Organic Letters
Organic Chemistry

Search outside of DiVA

GoogleGoogle Scholar
Total: 40 downloads
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

Altmetric score

Total: 89 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf