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
Mild Silver-Mediated Geminal Difluorination of Styrenes Using an Air- and Moisture-Stable Fluoroiodane Reagent
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: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 53, no 47, 12897-12901 p.Article in journal (Refereed) Published
Abstract [en]

An air-and moisture-stable fluoroiodane in the presence of AgBF4 is suitable for selective geminal difluorination of styrenes under mild reaction conditions. One of the C-F bonds is formed by transfer of electrophilic fluorine from the hypervalent iodine reagent, while the other one arises from the tetrafluoroborate counterion of silver. Deuterium-isotope-labelling experiments and rearrangement of methyl styrene substrates suggest that the reaction proceeds through a phenonium ion intermediate.

Place, publisher, year, edition, pages
2014. Vol. 53, no 47, 12897-12901 p.
Keyword [en]
fluorine, hypervalent compounds, reaction mechanism, rearrangement, silver
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-121570DOI: 10.1002/anie.201408812ISI: 000344793400041OAI: oai:DiVA.org:su-121570DiVA: diva2:859896
Funder
Knut and Alice Wallenberg FoundationSwedish Research Council
Available from: 2015-10-09 Created: 2015-10-09 Last updated: 2017-12-01Bibliographically approved
In thesis
1. Novel Applications of Benziodoxole Reagents in the Synthesis of Organofluorine Compounds
Open this publication in new window or tab >>Novel Applications of Benziodoxole Reagents in the Synthesis of Organofluorine Compounds
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis concerns method development of new synthetic routes by applying electrophilic hypervalent iodine reagents, such as trifluoromethyl-benziodoxole (Togni reagent) and fluoro-benziodoxole. The first project involved the addition of an oxygen moiety and trifluoromethyl group across double and triple bonds (both groups derived from the hypervalent iodine reagent). We observed that electron donating substituents on the aromatic ring of the substrate accelerated the oxytrifluoromethylation reaction. This transformation was further expanded to halo-trifluoromethylation reaction of a vinyl silane substrate. We also developed a copper mediated cyanotrifluoromethylation reaction, which was accelerated by PCy3 additive. This transformation allowed for the creation of two new C-C bonds in a single addition reaction. The direct C-H trifluoromethylation reaction of quinones was achived using the Togni-reagent in the presence of B2pin2 additive. The intriguing additive effects of both B2pin2 and PCy3 inspired us to examine the mechanism of these transformations.

Fluoro-benziodoxole is the fluoroiodane analogue of the trifluoromethylating Togni reagent. We developed a AgBF4 mediated geminal difluorination of styrenes using this fluoroiodine reagent. In this process one fluorine atom came from the fluoroiodane, while the other fluorine was derived from the tetrafluoroborate ion. A similar approach was applied for the 1,3-oxyfluorination and difluorination of cyclopropanes. Similarly, this fluorinative ring opening of unactivated cyclopropanes involved the introduction of an electrophilic fluorine atom from the fluoroiodane reagent and a nucleophilic one from the tetrafluoroborate ion. This reaction was extended to synthesis of 1,3-oxyfluorinated products. When alkenes reacted with the fluoro-benziodoxole reagent in the presence of palladium catalyst the iodofluorination reaction occurred.  Both the iodine and fluorine atoms were derived from the fluoroiodane reagent. The iodofluorination reaction with disubstituted and cyclic alkenes proceeded with high regio- and stereoselectivity.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2017. 61 p.
Keyword
trifluoromethylation, hypervalent iodine, Togni reagent, difluorination, iodofluorination
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-136207 (URN)978-91-7649-618-3 (ISBN)978-91-7649-619-0 (ISBN)
Public defence
2017-02-10, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Available from: 2017-01-18 Created: 2016-12-01 Last updated: 2016-12-08Bibliographically approved

Open Access in DiVA

fulltext(366 kB)57 downloads
File information
File name FULLTEXT01.pdfFile size 366 kBChecksum SHA-512
aff4a5947642bc3a15eb6660cbd8c28bcd189bee3147a906ba16f164412265f88bbff10f6f0af38deb02b20b9c54e863a620547a6c335e03f729827c197cbda4
Type fulltextMimetype application/pdf

Other links

Publisher's full text

Search in DiVA

By author/editor
Ilchenko, Nadia O.Szabó, Kálmán J.
By organisation
Department of Organic Chemistry
In the same journal
Angewandte Chemie International Edition
Organic Chemistry

Search outside of DiVA

GoogleGoogle Scholar
Total: 57 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

doi
urn-nbn

Altmetric score

doi
urn-nbn
Total: 126 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