Sodium Triflinate Research Articles

ChemInform Abstract: Visible‐Light‐Induced Photocatalytic Azotrifluoromethylation of Alkenes with Aryldiazonium Salts and Sodium Triflinate.

AbstractThe reaction tolerates variously functionalized aryl diazonium salts as well as terminal, 1,1‐ and cyclic or acyclic 1,2‐disubstituted alkenes.

ChemInform Abstract: Operationally Simple Hydrotrifluoromethylation of Alkenes with Sodium Triflinate Enabled by Ir Photoredox Catalysis.

AbstractThe title reaction works well with terminal alkenes and yields anti‐Markovnikov products.

ChemInform Abstract: Pd‐Catalyzed Synthesis of Aryl and Heteroaryl Triflones from Reactions of Sodium Triflinate with Aryl (Heteroaryl) Triflates.

A novel method for Pd-catalyzed triflination of aryl and heteroaryl triflates using NaSO2CF3 as the nucleophile is described. The combination of Pd2(dba)3 and RockPhos formed the most effective catalyst. A broad range of functional groups and heteroaromatic compounds were tolerated under the neutral reaction conditions. The order of reactivity ArOTf ≥ ArCl ≥ ArBr is consistent with transmetalation being a slow step of the reaction.

Simple and Clean Photoinduced Aromatic Trifluoromethylation Reaction.

We describe a simple, metal- and oxidant-free photochemical strategy for the direct trifluoromethylation of unactivated arenes and heteroarenes under either ultraviolet or visible light irradiation. We demonstrated that photoexcited aliphatic ketones, such as acetone and diacetyl, can be used as promising low-cost radical initiators to generate CF3 radicals from sodium triflinate efficiently. The broad utility of this strategy and its benefit to medicinal chemistry are demonstrated by the direct trifluoromethylation of unprotected bidentate chelating ligand, xanthine alkaloids, nucleosides, and related antiviral drug molecules.

ChemInform Abstract: Silver‐Catalyzed Tandem Trifluoromethylation and Cyclization of Aryl Isonitriles with the Langlois Reagent.

Abstract6—(Trifluoromethyl)phenanthridines are prepared by oxidative cyclization of biaryl isonitriles with sodium triflinate.

Pd-Catalyzed Synthesis of Aryl and Heteroaryl Triflones from Reactions of Sodium Triflinate with Aryl (Heteroaryl) Triflates.

A novel method for Pd-catalyzed triflination of aryl and heteroaryl triflates using NaSO2CF3 as the nucleophile is described. The combination of Pd2(dba)3 and RockPhos formed the most effective catalyst. A broad range of functional groups and heteroaromatic compounds were tolerated under the neutral reaction conditions. The order of reactivity ArOTf ≥ ArCl ≥ ArBr is consistent with transmetalation being a slow step of the reaction.

Visible-light-induced photocatalytic azotrifluoromethylation of alkenes with aryldiazonium salts and sodium triflinate.

The efficient visible light photocatalytic azotrifluoromethylation of alkenes with aryldiazonium salts and sodium triflinate is described, which gave the corresponding trifluoromethylated azo compounds in generally good yields. The trifluoromethylated azo products can be easily transformed into useful heterocycles and nitrogen-containing building blocks.

Photoorganocatalysed and visible light photoredox catalysed trifluoromethylation of olefins and (hetero)aromatics in batch and continuous flow.

Trifluoromethylation of olefins and (hetero)aromatics with sodium triflinate as CF3 source and readily accessible benzophenone derivatives as photosensitisers has been developed in batch and flow. The use of an iridium-based photocatalyst enables the trifluoromethylation to proceed under visible light irradiation.

Operationally simple hydrotrifluoromethylation of alkenes with sodium triflinate enabled by Ir photoredox catalysis

We report herein a single component Ir photoredox catalyst which is capable of catalyzing the hydrotrifluoromethylation of terminal alkenes and Michael acceptors with sodium triflinate (Langlois reagent) in methanol under irradiation at room temperature. Various synthetically useful functional groups, including ester, amide, ether, aldehyde, sulfone, ketone and aryl boronate, are well tolerated in this reaction.

Silver-Catalyzed Tandem Trifluoromethylation and Cyclization of Aryl Isonitriles with the Langlois Reagent

A mild and efficient procedure for the silver-catalyzed tandem trifluoromethylation and cyclization of aryl isonitriles with the Langlois­ reagent (sodium triflinate) is developed. A series of trifluoromethylated phenanthridines is prepared in moderate to good yields from a cheap and stable trifluoromethyl source.

ChemInform Abstract: Direct Trifluoromethylation of Imidazoheterocycles in a Recyclable Medium at Room Temperature.

AbstractA green trifluoromethylation of heterocycle‐fused imidazoles by sodium triflinate in an ionic liquid/water mixture is reported.

ChemInform Abstract: Cascade Multicomponent Synthesis of Indoles, Pyrazoles, and Pyridazinones by Functionalization of Alkenes.

AbstractAn efficient synthesis of 2‐(2,2,2‐trifluoromethyl)‐substituted indoles is achieved by a three‐component reaction of aryldiazonium tetrafluoroborates, alkenes, and sodium triflinate.

Cascade multicomponent synthesis of indoles, pyrazoles, and pyridazinones by functionalization of alkenes.

The development of multicomponent reactions for indole synthesis is demanding and has hardly been explored. The present study describes the development of a novel multicomponent, cascade approach for indole synthesis. Various substituted indole derivatives were obtained from simple reagents, such as unfunctionalized alkenes, diazonium salts, and sodium triflinate, by using an established straightforward and regioselective method. The method is based on the radical trifluoromethylation of alkenes as an entry into Fischer indole synthesis. Besides indole synthesis, the application of the multicomponent cascade reaction to the synthesis of pyrazoles and pyridazinones is described.

Telomerization of vinylidene fluoride with alkyl (or aryl) trifluoromethanethiosulfonates

AbstractThe photochemical‐induced telomerization of vinylidene fluoride (VDF) with cyclohexyl (or phenyl) trifluoromethanethiosulfonate (CF3SO2SR), leading to CF3(VDF)nSR telomers, where R stands for cyclohexyl or phenyl, is presented. These sulfurated transfer agents were synthesized by the reaction between sodium triflinate (CF3SO2Na) and disulfide in the presence of bromine. 19F NMR spectroscopy enabled an assessment of the average degrees of telomerization (DPn) of these telomers with a neat CF3 end group as the label. These DPn values increased for higher [VDF]0/[CF3SO2SR]0 initial molar ratios. Interestingly, the normal/reversed ratio of VDF units in these telomers was low. Finally, the cotelomerization of VDF and hexafluoropropylene with these transfer agents was successfully achieved, leading to original ω‐CF3 fluoroelastomers, the thermal properties of which were investigated. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4538–4549, 2002

Improved synthesis of trifluoromethyl sulfones used as intermediates for the preparation of di- or tri-substituted olefins

Primary and secondary trifluoromethyl sulfones (triflones) are efficiently obtained from easily available sodium trifluoromethanesulfinate (triflinate) and alkyl bromides in N,N-dimethylacetamide. This technique is more powerful than the potassium triflinate/acetonitrile system. Ethyl aconitate can be also produced in one step from ethyl bromoacetate and diisopropylethylamine, sodium triflinate being a catalyst.