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Palladium-Catalyzed lodofluorination of Alkenes Using Fluorolodoxole Reagent
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.ORCID-id: 0000-0003-4299-8860
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.ORCID-id: 0000-0002-9349-7137
2016 (Engelska)Ingår i: ACS Catalysis, ISSN 2155-5435, E-ISSN 2155-5435, Vol. 6, nr 1, s. 447-450Artikel i tidskrift (Refereegranskat) Published
Abstract [en]

The application of an air- and moisture-stable fluoroiodane reagent was investigated in the palladium-catalyzed iodofluorination reaction of alkenes. Both the iodo and fluoro substituents arise from the fluoroiodane reagent. In the case of certain palladium catalysts, the alkene substrates undergo allylic rearrangement prior to the iodofluorination process. The reaction is faster for electron-rich alkenes than for electron-deficient ones.

Ort, förlag, år, upplaga, sidor
2016. Vol. 6, nr 1, s. 447-450
Nyckelord [en]
fluorination, hypervalent iodines, iodofluorination, palladium catalysis, alkenes, difunctionalization
Nationell ämneskategori
Organisk kemi
Forskningsämne
organisk kemi
Identifikatorer
URN: urn:nbn:se:su:diva-126379DOI: 10.1021/acscatal.5b02022ISI: 000367706800049OAI: oai:DiVA.org:su-126379DiVA, id: diva2:902962
Forskningsfinansiär
VetenskapsrådetKnut och Alice Wallenbergs StiftelseTillgänglig från: 2016-02-12 Skapad: 2016-02-01 Senast uppdaterad: 2019-12-16Bibliografiskt granskad
Ingår i avhandling
1. Novel Applications of Benziodoxole Reagents in the Synthesis of Organofluorine Compounds
Öppna denna publikation i ny flik eller fönster >>Novel Applications of Benziodoxole Reagents in the Synthesis of Organofluorine Compounds
2017 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
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.

Ort, förlag, år, upplaga, sidor
Stockholm: Department of Organic Chemistry, Stockholm University, 2017. s. 61
Nyckelord
trifluoromethylation, hypervalent iodine, Togni reagent, difluorination, iodofluorination
Nationell ämneskategori
Organisk kemi
Forskningsämne
organisk kemi
Identifikatorer
urn:nbn:se:su:diva-136207 (URN)978-91-7649-618-3 (ISBN)978-91-7649-619-0 (ISBN)
Disputation
2017-02-10, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (Engelska)
Opponent
Handledare
Tillgänglig från: 2017-01-18 Skapad: 2016-12-01 Senast uppdaterad: 2016-12-08Bibliografiskt granskad
2. Development of new Fluorination Methods Directed to Fluorine-18 Labelling
Öppna denna publikation i ny flik eller fönster >>Development of new Fluorination Methods Directed to Fluorine-18 Labelling
2019 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
Abstract [en]

This thesis deals with the development of new fluorination reactions and their application to fluorine-18 labelling. Fluorine-18 labelled compounds are employed as tracers in Positron Emission Tomography (PET), which is a powerful non-invasive imaging method in medical diagnostics.

The first part of this thesis focuses on the development of a late-stage halogen exchange-based fluorination method for the synthesis of trifluoromethylated molecules. The first project in this area relies on the application of a copper(I)-based fluorinating reagent to furnish trifluoroacetates, trifluorotoluenes and trifluoroacetamides. The second project involves the translation of this methodology into the fluorine-18 labelling of tertiary and secondary trifluoroacetamides. The targeted substrates were labelled in high radiochemical yield and high molar activity using [18F]Bu4NF as fluorine source in the presence of an organic activator.

In the second part, the development of electrophilic fluorination reactions using a hypervalent iodine-based reagent is discussed. The first project in this area addresses the development of an electrophilic fluorine-18 fluorination reagent: [18F]fluoro-benziodoxole. The utility of this reagent was demonstrated in the labelling of [18F]fluoro-benzoxazepines. In the second project, the same [18F]fluoro-benziodoxole reagent was used in the rhodium-mediated synthesis of α-[18F]fluoroethers. High molar activities were obtained in these electrophilic labelling processes. In the third project, the fluorine-19 analog fluoro-benziodoxole was used in the palladium-catalyzed iodofluorination of allyl benzenes, styrenes and cycloalkenes. Both iodine and fluorine atoms in the product arise from the same reagent.

Ort, förlag, år, upplaga, sidor
Sockholm: Department of Organic Chemistry, Stockholm University, 2019. s. 73
Nyckelord
fluorine, fluorine-18, late-stage, labelling, nucleophilic, electrophilic, fluorination, positron emision tomography, PET, hypervalent iodine, benziodoxole, metal-free, DBU, copper, palladium, rhodium, carbene
Nationell ämneskategori
Organisk kemi
Forskningsämne
organisk kemi
Identifikatorer
urn:nbn:se:su:diva-175601 (URN)978-91-7797-919-7 (ISBN)978-91-7797-920-3 (ISBN)
Disputation
2020-01-20, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 15:00 (Engelska)
Opponent
Handledare
Tillgänglig från: 2019-12-16 Skapad: 2019-11-05 Senast uppdaterad: 2019-11-27Bibliografiskt granskad

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Ilchenko, Nadia O.Cortés, Miguel A.Szabó, Kálmán J.
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