One-pot synthesis of trifluoromethyl amines and perfluoroalkyl amines with CF3SO2Na and RfSO2Na

Liang, Shuaishuai; Wei, Jingjing; Jiang, Lvqi; Liu, Jie; Mumtaz, Yasir; Yi, Wen‐Bin

doi:10.1039/c9cc03282g

Cited by 43 publications

(38 citation statements)

References 33 publications

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“…For a real test of our procedure, we chose t ert ‐butyl piperazine‐1‐carboxylate ( 12 ) that had been used previously, [2,9] and successfully obtained the N ‐trifluoromethyl analogue 13 in decent yields with our method. In contrast to the former reports, in which the product was described as an oil, we could isolate it as a crystalline colorless substance, clearly demonstrating one of the advantages of our method for this particular substrate.…”

Section: Resultsmentioning

confidence: 99%

“…A similar process had been observed previously for the synthesis of CF 3 -ethers, [4b,8] however, to the best of our knowl-edge, the reaction of monomeric N-dithiocarbamate-organyls and their conversion via AgF to N-CF 3 groups had not been reported so far. [1b] For a real test of our procedure, we chose tert-butyl piperazine-1-carboxylate (12) that had been used previously, [2,9] and successfully obtained the N-trifluoromethyl analogue 13 in decent yields with our method. In contrast to the former reports, in which the product was described as an oil, we could isolate it as a crystalline colorless substance, clearly demonstrating one of the advantages of our method for this particular substrate.…”

Section: Chemistryselectmentioning

confidence: 99%

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A Facile and Inexpensive Way to Synthesize N‐trifluoromethyl Compounds

2022

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A facile way to introduce CF3 groups on a large variety of secondary amines has been developed, avoiding expensive and hazardous reagents. The advantage of the method could be demonstrated by obtaining crystalline tert‐butyl 4‐(trifluoromethyl)piperazine‐1‐carboxylate, a compound that previously only had been obtained as an oil. A major problem is the extreme sensitivity of these compounds towards moisture.

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Section: Resultsmentioning

confidence: 99%

Section: Chemistryselectmentioning

confidence: 99%

A Facile and Inexpensive Way to Synthesize N‐trifluoromethyl Compounds

2022

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“…In contrast to perfluoroalkyl and perfluoroalkoxy groups, the chemistry of related perfluoroalkyl nitrogen substituents has been studied to a much lesser extent. Some synthetic strategies towards N ‐trifluoromethylamines and related N ‐perfluoroalkylnitrogen derivates have been developed in recent years [28–38] . Efficient strategies towards N , N ‐bis(perfluoroalkyl)nitrogen compounds remain scarce, presumably, because of the lack of suitable starting materials [18,39–40] .…”

Section: Figurementioning

confidence: 99%

“…Some synthetic strategies towards N ‐trifluoromethylamines and related N ‐perfluoroalkylnitrogen derivates have been developed in recent years. [ 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 ] Efficient strategies towards N , N ‐bis(perfluoroalkyl)nitrogen compounds remain scarce, presumably, because of the lack of suitable starting materials. [ 18 , 39 , 40 ] Especially the N , N ‐bis(trifluoromethyl)amino group is of interest as its organic derivatives are known to exhibit high stability, for example against acids and bases,[ 1 , 41 ] and because its potential as substituent in pharmaceuticals was demonstrated, earlier.…”

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confidence: 99%

Stable and Storable N(CF₃)₂ Transfer Reagents

Schneider

Krauel

Deutsch

et al. 2021

Chemistry A European J

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Fluorinated groups are essential for drug design, agrochemicals, and materials science. The bis(trifluoromethyl) amino group is an example of a stable group that has a high potential. While the number of molecules containing perfluoroalkyl, perfluoroalkoxy, and other fluorinated groups is steadily increasing, examples with the N(CF 3 ) 2 group are rare. One reason is that transfer reagents are scarce and metalbased storable reagents are unknown. Herein, a set of Cu I and Ag I bis(trifluoromethyl)amido complexes stabilized by N-and P-donor ligands with unprecedented stability are presented. The complexes are stable solids that can even be manipulated in air for a short time. They are bis(trifluoromethyl) amination reagents as shown by nucleophilic substitution and Sandmeyer reactions. In addition to a series of benzylbis (trifluoromethyl)amines, 2-bis(trifluoromethyl)amino acetate was obtained, which, upon hydrolysis, gives the fluorinated amino acid N,N-bis(trifluoromethyl)glycine.Transition metal perfluoroalkyl complexes are highly valuable reagents for the synthesis of fluorinated biologically active molecules that are employed as pharmaceuticals or agrochemicals and in materials applications. [1][2][3][4][5][6] Especially, copper(I) complexes are important as they enable the introduction of a broad variety of perfluoroalkyl groups into organic molecules that range from the simplest congener, trifluoromethyl, to longer linear and branched perfluoroalkyl groups such as the heptafluoroisopropyl (hfip) group. [7][8][9][10] Although many of these complexes are used either in situ or immediately after generation, some complexes have been isolated and characterized, in detail. These complexes are often stabilized by co-ligands that typically are pyridines or phosphanes, for example [(bpy)CuC 2 F 5 ] (Figure 1) [11] and [(Ph 3 P) 2 Cu{CF(CF 3 ) 2 }] ([(Ph 3 P) 2 Cu(hfip)]). [12] Silver (I) complexes have been employed as perfluoroalkylation reagents as well, [13][14] although to a lesser extent than the related copper(I) derivatives. Because of their easy accessibility using silver(I) fluoride and the respective perfluoroalkene, for example, heptafluoropropene and tetrafluoroethylene, [15] they[a] L.

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“…The latter can also be generated starting from AgSCF 3 in conjunction with potassium bromide (Scheme , III ). More recently, the group of Jiang and Yi demonstrated that the Langlois reagent could also be used in conjunction with triphenylphosphine to form thiocarbamoyl fluorides (Scheme , IV ) . In this context, we thought that the straightforward synthesis of thiocarbamoyl fluoride through fluorinative desulfurization would constitute an attractive option for the access thiocarbamoyl fluorides.…”

Section: Introductionmentioning

confidence: 99%

Direct Synthesis of Thiocarbamoyl Fluorides and Trifluoromethylamines Through Fluorinative Desulfurization

2019

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Herein, a straightforward synthesis of thiocarbamoyl fluorides is reported starting from amines and carbon disulfide. The key to success is the fluorinative desulfurization of carbon disulfide with (diethylamino)sulfur trifluoride (DAST). The title compounds were obtained in moderate to very good isolated yields. Furthermore, we demonstrated also that thiocarbamoyl fluoride can be converted into their trifluoromethylamine analogues through simple treatment with silver fluoride.

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One-pot synthesis of trifluoromethyl amines and perfluoroalkyl amines with CF₃SO₂Na and R_fSO₂Na

Abstract: Novel use of CF3SO2Na and RfSO2Na for the synthesis of trifluoromethyl amines and perfluoroalkyl amines was developed.

Cited by 43 publications

References 33 publications

A Facile and Inexpensive Way to Synthesize N‐trifluoromethyl Compounds

A Facile and Inexpensive Way to Synthesize N‐trifluoromethyl Compounds

Stable and Storable N(CF₃)₂ Transfer Reagents

Direct Synthesis of Thiocarbamoyl Fluorides and Trifluoromethylamines Through Fluorinative Desulfurization

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One-pot synthesis of trifluoromethyl amines and perfluoroalkyl amines with CF3SO2Na and RfSO2Na

Abstract: Novel use of CF3SO2Na and RfSO2Na for the synthesis of trifluoromethyl amines and perfluoroalkyl amines was developed.

Cited by 43 publications

References 33 publications

A Facile and Inexpensive Way to Synthesize N‐trifluoromethyl Compounds

A Facile and Inexpensive Way to Synthesize N‐trifluoromethyl Compounds

Stable and Storable N(CF3)2 Transfer Reagents

Direct Synthesis of Thiocarbamoyl Fluorides and Trifluoromethylamines Through Fluorinative Desulfurization

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One-pot synthesis of trifluoromethyl amines and perfluoroalkyl amines with CF₃SO₂Na and R_fSO₂Na

Stable and Storable N(CF₃)₂ Transfer Reagents