title: Expanding the Scope of Hypervalent Iodine Reagents for Perfluoroalkylation: From Trifluoromethyl to Functionalized Perfluoroethyl.
abstract: A series of new hypervalent iodine reagents based on the 1,3-dihydro-3,3-dimethyl-1,2-benziodoxole and 1,2-benziodoxol-3-(1H)-one scaffolds, which contain a functionalized tetrafluoroethyl group, have been prepared, characterized, and used in synthetic applications. Their corresponding electrophilic fluoroalkylation reactions with various sulfur, oxygen, phosphorus, and carbon-centered nucleophiles afford products that feature a tetrafluoroethylene unit, which connects two functional moieties. A related λ(3) -iodane that contains a fluorophore was shown to react with a cysteine derivative under mild conditions to give a thiol-tagged product that is stable in the presence of excess thiol. Therefore, these new reagents show a significant potential for applications in chemical biology as tools for fast, irreversible, and selective thiol bioconjugation.
authors.affiliation: Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology, ETH Zürich, Vladimir-Prelog-Weg 2, 8093 Zürich (Switzerland).
authors.forename: Václav
authors.initials: V
authors.lastname: Matoušek
authors.affiliation: Institute of Organic Chemistry and Biochemistry, v.v.i., Academy of Sciences of the Czech Republic, Flemingovo nám. 2, 166 10 Prague (Czech Republic).|Laboratory of Molecular Structure Characterization, Institute of Microbiology, v.v.i., Academy of Sciences of the Czech Republic, Vídeňská 1083, 142 20 Prague (Czech Republic).
authors.forename: Jiří
authors.initials: J
authors.lastname: Václavík
authors.affiliation: Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology, ETH Zürich, Vladimir-Prelog-Weg 2, 8093 Zürich (Switzerland).
authors.forename: Peter
authors.initials: P
authors.lastname: Hájek
authors.affiliation: Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology, ETH Zürich, Vladimir-Prelog-Weg 2, 8093 Zürich (Switzerland).
authors.forename: Julie
authors.initials: J
authors.lastname: Charpentier
authors.affiliation: Institute of Organic Chemistry and Biochemistry, v.v.i., Academy of Sciences of the Czech Republic, Flemingovo nám. 2, 166 10 Prague (Czech Republic).
authors.forename: Zsófia E
authors.initials: ZE
authors.lastname: Blastik
authors.affiliation: Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology, ETH Zürich, Vladimir-Prelog-Weg 2, 8093 Zürich (Switzerland).
authors.forename: Ewa
authors.initials: E
authors.lastname: Pietrasiak
authors.affiliation: Institute of Organic Chemistry and Biochemistry, v.v.i., Academy of Sciences of the Czech Republic, Flemingovo nám. 2, 166 10 Prague (Czech Republic).
authors.forename: Alena
authors.initials: A
authors.lastname: Budinská
authors.affiliation: Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology, ETH Zürich, Vladimir-Prelog-Weg 2, 8093 Zürich (Switzerland). atogni@ethz.ch.
authors.forename: Antonio
authors.initials: A
authors.lastname: Togni
authors.affiliation: Institute of Organic Chemistry and Biochemistry, v.v.i., Academy of Sciences of the Czech Republic, Flemingovo nám. 2, 166 10 Prague (Czech Republic). beier@uochb.cas.cz.
authors.forename: Petr
authors.initials: P
authors.lastname: Beier
keywords: bioconjugation; fluorine; fluoroalkylation; hypervalent compounds; iodine; tetrafluoroethylene