Endre søk
RefereraExporteraLink to record
Permanent link

Direct link
Referera
Referensformat
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Annet format
Fler format
Språk
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Annet språk
Fler språk
Utmatningsformat
  • html
  • text
  • asciidoc
  • rtf
Mild Silver-Mediated Geminal Difluorination of Styrenes Using an Air- and Moisture-Stable Fluoroiodane Reagent
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.ORCID-id: 0000-0002-9349-7137
2014 (engelsk)Inngår i: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 53, nr 47, s. 12897-12901Artikkel i tidsskrift (Fagfellevurdert) 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.

sted, utgiver, år, opplag, sider
2014. Vol. 53, nr 47, s. 12897-12901
Emneord [en]
fluorine, hypervalent compounds, reaction mechanism, rearrangement, silver
HSV kategori
Forskningsprogram
organisk kemi
Identifikatorer
URN: urn:nbn:se:su:diva-121570DOI: 10.1002/anie.201408812ISI: 000344793400041OAI: oai:DiVA.org:su-121570DiVA, id: diva2:859896
Forskningsfinansiär
Knut and Alice Wallenberg FoundationSwedish Research CouncilTilgjengelig fra: 2015-10-09 Laget: 2015-10-09 Sist oppdatert: 2019-12-16bibliografisk kontrollert
Inngår i avhandling
1. Novel Applications of Benziodoxole Reagents in the Synthesis of Organofluorine Compounds
Åpne denne publikasjonen i ny fane eller vindu >>Novel Applications of Benziodoxole Reagents in the Synthesis of Organofluorine Compounds
2017 (engelsk)Doktoravhandling, med artikler (Annet vitenskapelig)
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.

sted, utgiver, år, opplag, sider
Stockholm: Department of Organic Chemistry, Stockholm University, 2017. s. 61
Emneord
trifluoromethylation, hypervalent iodine, Togni reagent, difluorination, iodofluorination
HSV kategori
Forskningsprogram
organisk kemi
Identifikatorer
urn:nbn:se:su:diva-136207 (URN)978-91-7649-618-3 (ISBN)978-91-7649-619-0 (ISBN)
Disputas
2017-02-10, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (engelsk)
Opponent
Veileder
Tilgjengelig fra: 2017-01-18 Laget: 2016-12-01 Sist oppdatert: 2016-12-08bibliografisk kontrollert

Open Access i DiVA

fulltext(366 kB)114 nedlastinger
Filinformasjon
Fil FULLTEXT01.pdfFilstørrelse 366 kBChecksum SHA-512
aff4a5947642bc3a15eb6660cbd8c28bcd189bee3147a906ba16f164412265f88bbff10f6f0af38deb02b20b9c54e863a620547a6c335e03f729827c197cbda4
Type fulltextMimetype application/pdf

Andre lenker

Forlagets fulltekst

Søk i DiVA

Av forfatter/redaktør
Ilchenko, Nadia O.Szabó, Kálmán J.
Av organisasjonen
I samme tidsskrift
Angewandte Chemie International Edition

Søk utenfor DiVA

GoogleGoogle Scholar
Totalt: 114 nedlastinger
Antall nedlastinger er summen av alle nedlastinger av alle fulltekster. Det kan for eksempel være tidligere versjoner som er ikke lenger tilgjengelige

doi
urn-nbn

Altmetric

doi
urn-nbn
Totalt: 178 treff
RefereraExporteraLink to record
Permanent link

Direct link
Referera
Referensformat
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Annet format
Fler format
Språk
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Annet språk
Fler språk
Utmatningsformat
  • html
  • text
  • asciidoc
  • rtf