⿢Trifluorination of aryl alkyl sulfides was performed with IF5-pyridine-HF.⿢The reaction was carried out at 80 °C.⿢Introduction of methyl group to the aryl group was effective.⿢The trifluorinated products were also formed from dithioketals.Stable fluorinating reagent, IF5-pyridine-HF, was used for the polyfluorination of aryl alkyl sulfides. The introduction of three fluorine atoms with a concomitant migration of the arylsulfanyl group was achieved. Carrying out the reaction at 80 °C and presence of a methyl substituent on the aryl group were found to be effective for the polyfluorination. Trifluorinated products were also obtained from dithioketals by reaction with IF5-pyridine-HF. Tetrafluorination of phenyl benzyl ketone and dibenzyl ketone dithioketals was also achieved by reaction with IF5-pyridine-HF and Et3N-6HF.

•Iodofluorination of alkyne was carried out.•IF species was generated from IF5-pyridine-HF.•Hydroquinone was found to be suitable as a reductant.•Reaction proceeded stereoselectively.•The resulting iodofluoroalkenes were used for the synthesis of fluoroalkenes.The iodofluorination of alkynes was carried out using IF5-pyridine-HF and hydroquinone. The iodofluorination of an internal alkyne and a terminal alkyne proceeded stereoselectively to give the corresponding iodofluoroalkenes. An unsymmetrically substituted internal alkyne and electron deficient alkyne also afforded the corresponding iodofluoroalkenes stereoselectively. The iodofluoroalkenes thus obtained were used in the stereoselective synthesis of di- and trisubstituted fluoroalkenes.

•An air-stable fluorinating reagent was prepared from BrF3 and KHF2.•BrF3–KHF2 was used in the various fluorination reactions.•Desulfurizing fluorination reactions of benzylic sulfides, dithioacetals and trimethyl trithioorthocarboxylates were performed.BrF3–KHF2, an air-stable solid prepared from BrF3 and KHF2, was used in the various fluorination reactions, including desulfurizing fluorination reactions of benzylic sulfides, ketone and aldehyde dithioacetals, (phenylthio)glycosides, and trimethyl trithioorthocarboxylates. As the results, one to three fluorine atoms were selectively introduced to the substrates.

•Fluoromethyl ethers were synthesized from the corresponding methylthiomethyl ethers.•A stable fluorination reagent, IF5-pyridine-HF, was used for the reaction.•Fluoromethyl ester was also synthesized in a similar way.•O-Fluoromethyl ether of a L-tyrosine derivative was synthesized by this method.Fluoromethyl ethers of various functionalized phenols were synthesized from the corresponding methylthiomethyl ethers by the reaction with IF5-pyridine-HF. A fluoromethyl ether of an aliphatic alcohol and a fluoromethyl ester of a carboxylic acid were also synthesized.

The direct fluorination reaction of the functionalized adamantanes was achieved by using BrF3. In the reaction with methyl adamantane-1-caroxylate 1 and dimethyl adamantane-1,3-dicarboxylate 3, three and two fluorine atoms, respectively, were introduced selectively to their tert-carbons. On the other hand, in the reactions with 1-acetoxymethyladamantane 5, and 2-adamantanone 9, not only the expected fluorination of their tert-carbons, but also unexpected reactions such as fluorination of carbonyl functionality occurred.Graphical abstractHighlights► Fluorination of functionalized adamantanes was performed with BrF3. ► Three to two fluorine atoms were selectively introduced to their tert-carbons. ► From methyl adamantane-1-carboxylate, methyl 3,5,7-trifluoroadamantane-1-carboxylate was selectively formed. ► Unexpected reactions, such as fluorination of carbonyl group, also occurred.

Trisubstituted (2-fluoroalkenyl)iodonium salts were prepared E- or Z-selectively by the reaction of (fluoroalkenyl)iodonium ylides generated from (fluoroalkenyl)iodonium salts with aldehydes.Graphical abstractHighlights► The reaction of (fluoroalkenyl)iodonium salt with LDA gave (fluoroalkenyl)iodonium ylide. ► Trisubstituted (fluoroalkenyl)iodonium salt was formed by the reaction of the (fluoroalkenyl)iodonium ylide with aldehyde. ► The reaction proceeds stereoselectively without losing its original stereochemistry. ► Both (E)- and (Z)-isomers can be prepared selectively.

An MT-sulfone group was converted to a trifluoromethyl group by treatment with IF5 after an alkylation reaction. Therefore, an MT-sulfone anion can be used as a trifluoromethyl anion equivalent. The formal asymmetric Michael-addition of a trifluoromethyl anion to crotonaldehyde was also performed.

Introduction of a polyfluoroalkyl group into aromatic compounds was achieved by Friedel-Crafts reaction using (1-chloro-1-hydroperfluoroalkyl) sulfides 1, and the subsequent desulfurizing–difluorination of the resulting product using IF5/Et3N-nHF. Perfluoroethyl, 1,1,2,2,3,3-hexafluoropropyl, and 1,1,2,2,3,3,4,4,5,5-decafluoropentyl groups were introduced to various aromatic compounds by this method. Selective perfluoroethylation of uracil at the 5-position was also performed.Graphical abstractHighlights► Perfluoroethyl, hexafluoropropyl, and decafluoropentyl groups were introduced to various aromatic compounds. ► Starting material can be prepared from commercially available alcohols. ► Perfluoroethyl group was selectively introduced at the 5-position of uracil using our method.

The deoxyfluorination reaction of β-diketones with N,N-diethyl-α,α-difluoro-m-methylbenzylamine (DFMBA) gave β-fluoro-α,β-unsaturated ketones in good yields. The reaction proceeded regioselectively, and only one regioisomer was obtained from the unsymmetrical 1-aryl-1,3-diketones. The reaction is applicable to diketones with a trifluoromethyl group, obtaining good yields of 3,4,4,4-tetrafluorobutenones. We used the resulting β-fluoro-α,β-unsaturated ketones for the reaction with lithium dialkyl cuprates.

We prepared a novel fluorous deoxy-fluorination reagent N,N-diethyl-α,α-difluoro-[3,5-bis(1H,1H,2H,2H-perfluorodecyl)benzyl]amine (1b) from 3,5-diiodobenzoic acid (3b) via N,N-diethyl-3,5-bis(1H,1H,2H,2H-perfluorodecyl)benzamide (2b) in four steps and used it for the fluorination of alcohols and diols. After the fluorination reactions, the isolation of the products and recovery of 2b was performed by extraction with a fluorous/organic solvent system.A fluorous deoxy-fluorination reagent N,N-diethyl-α,α-difluoro-[3,5-bis(1H,1H,2H,2H-perfluorodecyl)benzyl]amine.

An MT-sulfone group was converted to a trifluoromethyl group by treatment with IF5 after an alkylation reaction. Therefore, an MT-sulfone anion can be used as a trifluoromethyl anion equivalent. The formal asymmetric Michael-addition of a trifluoromethyl anion to crotonaldehyde was also performed.