Substituent-controlled, mild oxidative fluorination of iodoarenes: synthesis and structural study of aryl I(iii)- and I(v)-fluorides

Abstract

This mild TCICA/KF oxidative fluorination approach provides controllable access to aryl-IF2 and aryl-IF4 compounds, thus allowing detailed structural studies.

Difluoro(aryl)(perfluoroalkyl)‐λ4‐sulfanes and Selanes: Missing Links of Trichloroisocyanuric Acid/Potassium Fluoride Chemistry

“…The trichloroisocyanuric acid/potassium fluoride (TCICA/KF) approach to oxidative fluorination has opened up new frontiers in the synthesis and study of highly fluorinated substituents. Recently, TCICA/KF conditions have 1) obviated the reliance on corrosive Cl 2 gas in the synthesis of aryl‐SF 4 Cl and aryl‐SF 3 compounds, 2) replaced XeF 2 in the synthesis of aryl‐SeF 3 and aryl‐TeF 5 compounds, and 3) circumvented extremely hazardous reagents such as F 2 , HF, and SF 4 in the synthesis of aryl‐IF 2 and aryl‐IF 4 compounds, thus demonstrating a powerful ability to make fluorination chemistry more accessible to the broader chemical community. Moreover, this approach has created opportunities to synthesize/study previously unknown fluorinated moieties, including the TeF 4 CF 3 group .…”

“…Recently, TCICA/KF conditions have 1) obviated the reliance on corrosive Cl 2 gas in the synthesis of aryl‐SF 4 Cl and aryl‐SF 3 compounds, 2) replaced XeF 2 in the synthesis of aryl‐SeF 3 and aryl‐TeF 5 compounds, and 3) circumvented extremely hazardous reagents such as F 2 , HF, and SF 4 in the synthesis of aryl‐IF 2 and aryl‐IF 4 compounds, thus demonstrating a powerful ability to make fluorination chemistry more accessible to the broader chemical community. Moreover, this approach has created opportunities to synthesize/study previously unknown fluorinated moieties, including the TeF 4 CF 3 group . Beyond academic interest, unknown/underexplored fluorinated groups of the like may find interesting applications in medicinal chemistry, agrochemistry, materials, or reagent design …”

“…The trichloroisocyanuric acid/potassium fluoride (TCICA/ KF) approach to oxidative fluorination has opened up new frontiers in the synthesis and study of highly fluorinated substituents.R ecently,T CICA/KF conditions have 1) obviated the reliance on corrosive Cl 2 gas in the synthesis of aryl-SF 4 Cl and aryl-SF 3 compounds, [1] 2) replaced XeF 2 in the synthesis of aryl-SeF 3 and aryl-TeF 5 compounds, [1,2] and 3) circumvented extremely hazardous reagents such as F 2 , HF,a nd SF 4 in the synthesis of aryl-IF 2 and aryl-IF 4 compounds, [3] thus demonstrating apowerful ability to make fluorination chemistry more accessible to the broader chemical community.M oreover,t his approach has created opportunities to synthesize/study previously unknown fluorinated moieties,i ncluding the Te F 4 CF 3 group. [3] Beyond academic interest, unknown/underexplored fluorinated groups of the like may find interesting applications in medicinal chemistry, agrochemistry,m aterials,orreagent design. [4,5] Following the chalcogen series,t he reactivity of diaryl disulfides, [1] diaryl diselenides, [1] and diaryl ditellurides [2] under TCICA/KF conditions has been studied in our laboratory,aswell as the behavior of aryl(trifluoromethyl)tellanes ( Figure 1).…”

Difluor(aryl)(perfluoralkyl)‐λ4‐Sulfane und Selane: Fehlende Bindeglieder der Trichlorisocyanursäure/Kaliumfluorid Chemie

“…Das Tr ichlorisocyanursäure/Kaliumfluorid(TCICA/KF)-System zur oxidativen Fluorierung hat neue Wege zur Synthese und Untersuchung von hochfluorierten Verbindungen erçffnet. Die Verwendung des TCICA/KF-Systems hat kürzlich ermçglicht 1) die Verwendung von Cl 2 -Gas bei der Synthese von Aryl-SF 4 Cl und Aryl-SF 3 -Verbindungen zu vermeiden, [1] 2) Aryl-SeF 3 und Aryl-TeF 5 ohne XeF 2 herzustellen [1,2] und 3) den Einsatz von extrem gefährlichen Reagenzien wie F 2 ,H Fu nd SF 4 bei der Synthese von Aryl-IF 2und Aryl-IF 4 -Verbindungen [3] zu umgehen. Infolgedessen hat das System die Fähigkeit bewiesen Fluorchemie einer breiteren chemischen Gesellschaft zugänglich zu machen.…”

“…Wei-terhin erlaubte es bislang unbekannte fluorierte Gruppen, wie die Te F 4 CF 3 -Gruppe,zusynthetisieren und zu untersuchen. [3] Neben rein wissenschaftlicher Neugier kçnnten solche Gruppen Anwendung in den Gebieten der medizinischen Chemie,A grochemie,M aterialwissenschaft oder beim Reagenzdesign finden. [4,5] Der Chalkogengruppe folgend haben wir die Reaktivitäten von Disulfiden, [1] Diaryldiseleniden [1] und Diarylditelluriden, [2] sowie Aryl(trifluormethyl)tellanen in Bezug auf das TCICA/KF-System untersucht (Abbildung 1).…”