Uses of the Trifyl Group in Organic Synthesis. A Review

Hendrickson, James B.; Bair, Kenneth W.; Bergeron, Raymond J.; Giga, A.; Skipper, Paul L.; Sternbach, Daniel D.; Wareing, James A.

doi:10.1080/00304947709356878

Cited by 30 publications

(13 citation statements)

References 16 publications

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“…The observed difference is typical of covalently bonded and anionic trifluoromethanesulfonate species [15]. The downfield shift of signals in the 1 H NMR spectrum of salt Ig relative to Ia (see above) is the stronger, the closer is the corresponding group to the charged [NCN] + fragment: Δδ We also tried to obtain DBU and DBN bis(trifluoromethylsulfonyl)imide ionic liquids directly in one step by reaction of the corresponding bases with N-phenyltrifluoromethanesulfonimide (CF 3 SO 2 ) 2 NPh (III) which was prepared according to the procedure described in [16]. The reaction in chloroform or methylene chloride was accompanied by heat evolution and strong tarring.…”

Section: Methodsmentioning

confidence: 99%

Trifluoromethanesulfonate, trifluromethylsulfonylimide, and bis(trifluoromethylsulfonyl)imide salts and ionic liquids based on 1,8-diazabicyclo[5.4.0]undec-7-ene and 1,5-diazabicyclo[ 4.3.0]non-5-ene

2010

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Trifluoromethanesulfonate, trifluoromethylsulfonylimide, and bis(trifluoromethylsulfonyl)imide salts and ionic liquids were synthesized from 2, 3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine (1,8-diazabicyclo[5.4.0]undec-7-ene) and 2, 3,4,6,7,8-hexahydropyrrolo[1,2-a]pyrimidine (1,5-diazabicyclo[4.3.0]non-5-ene). Their physicochemical properties, spectral parameters, and some chemical transformations were studied. I, II, X = H: Y = F 3 CSO 2 O (a), F 3 CSO 2 NH (b), (F 3 CSO 2 ) 2 N (c); X = Pr: Y = Cl (d), (F 3 CSO 2 ) 2 N (e); X = Ph, Y = (F 3 CSO 2 ) 2 N (f); X = F 3 CSO 2 , Y = F 3 CSO 2 O (g).First ionic liquids based on 1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU,2,3,4,6,7,8,9,azepine) cations and various anions (Cl, Br, OTs, OTf) were reported previously [1-3]. Of particular interest are ionic liquids containing bis(trifluoromethylsulfonyl)imide anion (CF 3 SO 2 ) 2 N -which considerably reduces the melting point and viscosity of ionic liquids, as compared to other anions. In addition, organic salts with trifluoromethylsulfonylimide and other perfluoroalkylsulfonylimide anions are mainly hydrophobic and are characterized by high thermal and electrochemical stability [4][5][6]. First ionic liquids with trifluoromethylsulfonylimide anion were synthesized on the basis of imidazolium cation in 1995-96 [7, 8], and they subsequently found wide application [9][10][11].In the present communication we describe the synthesis of new salts and ionic liquids derived from DBU (I) and 1,5-diazabicyclo[4.3.0]non-5-ene (II, DBN, 2,3,4,6,7,8-hexahydropyrrolo[1,2-a]pyrimidine) and containing trifluoromethanesulfonate, trifluoromethylsulfonylimide, and bis(trifluoromethylsulfonyl)imide anions. The initial nitrogen-containing bases, DBU and DBN, are readily obtained from ε-caprolactam and pyrrolidin-2-one, respectively, and their synthetic and commercial accessibilities are quite comparable with those of 1-alkylimidazoles that are starting compounds for the preparation of most known ionic liquids.Almost similar structures of DBU (I) and DBN (II) in salts (X = N) and ionic liquids (X = R) makes it possible to use spectral parameters of readily obtainable and identifiable salts DBUH + Y -and DBNH + Yfor identification of ionic liquids DBUR + Y -and DBNR + Y -which are synthesized by different methods.Trifluoromethanesulfonate, trifluoromethylsulfonylimide, and bis(trifluoromethylsulfonyl)imide DBU and DBN salts Ia-Ic and IIa-IIc were prepared in quantitative yield by mixing equimolar amounts of the corresponding base and trifluoromethanesulfonic acid CF 3 SO 3 H, trifluoromethanesulfonamide CF 3 S O 2 NH 2 , o r t r i f luo r o me t h a n s u l f o n i mi d e (CF 3 SO 2 ) 2 NH under solvent-free conditions or in chloroform at room temperature. The products were analyzed after removal of the solvent without additional purification. The isolated salts were colorless

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Section: Methodsmentioning

confidence: 99%

Trifluoromethanesulfonate, trifluromethylsulfonylimide, and bis(trifluoromethylsulfonyl)imide salts and ionic liquids based on 1,8-diazabicyclo[5.4.0]undec-7-ene and 1,5-diazabicyclo[ 4.3.0]non-5-ene

2010

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“…Two main methods of synthesis of triflamides and other perfluoroalkanesulfonamides have been described: The reaction of the corresponding fluoroalkylsulfonyl fluorides RFSO 2 F with ammonia or amines, [1][2][3][4][5][6] and the raction of trifluoromethanesulfonyl chloride CF 3 SO 2 Cl or triflic anhydride (CF 3 SO 2 ) 2 O normally, in the presence of triethylamine to bind the eliminated triflic acid. [7][8][9] Different approaches based on the Mitsunobu reaction 10) and the intermolecular bromoesterification of allylic sulfonamides have also been reported. 11) However, the majority of these reactions have disadvantages such as: poor yield, multiple reaction steps, difficulty to workup, and the use of an excess of amine is required.…”

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confidence: 99%

An Efficient Strategy for the Synthesis of 1-(Trifluoromethylsulfonamido)propan-2-yl Esters and the Evaluation of Their Cytotoxic Activity

Gómez-García¹,

Gómez²,

Monzón-González³

et al. 2017

Chem. Pharm. Bull.

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An efficient method for the synthesis of 1-(trifluoromethylsulfonamido)propan-2-yl benzoates is described, the products of the reaction were characterized by heteronuclear single quantum coherence spectroscopy (HSQC), heteronuclear multiple bond correlation (HMBC) and NMR experiments. The overall process began with the activation of the oxazoline ring by triflic anhydride, followed by the opening of the five-membered ring in the 5-methyl-2-phenyl-4,5-dihydrooxazole system. The cytotoxic activity of the new trifluoromethyl sulfonamides was evaluated with six cancer cell lines and human gingival fibroblasts, posteriorly analyzing the influence on cytotoxicity exerted by the withdrawing and donor substituents at the para-position of the phenyl ring. Compounds 3b-e showed cytotoxic activity, with IC 50 values ranging from 17-17.44 µM for the cell lines tested, finding the highest effect for compound 3e.

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“…We were intrigued by a report from Hendrickson and Bair that explored the use of reagents such as triflic anhydride and N-phenyl triflimide (2.11) for the synthesis of triflones. 36,37 The treatment of triflic anhydride with sec-butyllithium yielded 43% sec-butyl triflone 2.18, as well as an unreported amount of ditriflinated product. However, the reaction of N-phenyl triflimide with sec-butyllithium gave a 67% yield of sec-butyl triflone 2.18 and no traces of ditriflinated products.…”

Section: Project Goalsmentioning

confidence: 99%

Development of Palladium-Catalyzed Decarboxylative Allylation of Electron-Deficient Sulfones: Method Development and Mechanistic Studies

Gill¹

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Palladium-catalyzed decarboxylative allylation is a powerful method of carbon-carbon bond construction. This methodology relies on an electronwithdrawing group to promote the reaction. The use of sulfones in decarboxylative allylation has been explored using the trifluoromethylsulfonyl (triflyl) group, as well as the bis(3,5-trifluoromethyl)phenylsulfonyl (BTMP) group. These substrates are highly reactive at room temperature (triflyl) and 50 o C (BTMP sulfones). A detailed mechanistic study using deuterium-labelled substrates was performed to understand the origin of the protonation side-product. It was proposed that a βhydride elimination from the η 1 allyl on palladium could generate a palladium hydride intermediate along with an allene. Although small amounts of deuterium incorporation were observed in the protonated products, the proposed mechanism could not be the major pathway. Using isotopically labelled ligand, however, all protonation was supressed. This suggests that the origin of the proton is actually from the ligand and that kinetic isotope effects may be responsible for inhibiting the protonation pathway with labelled ligand. HRMS: m/z calcd for C14H12O2F6S: 358.0462; Found: 358.0454. But-2-en-1-yl-2-((3,5-bis(trifluoromethyl)phenyl)thio)acetate (3.37) Reaction Time & Temperature: 45 min, 80 °C Base: Pyridine Yield: 75%.

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Uses of the Trifyl Group in Organic Synthesis. A Review

Cited by 30 publications

References 16 publications

Trifluoromethanesulfonate, trifluromethylsulfonylimide, and bis(trifluoromethylsulfonyl)imide salts and ionic liquids based on 1,8-diazabicyclo[5.4.0]undec-7-ene and 1,5-diazabicyclo[ 4.3.0]non-5-ene

Trifluoromethanesulfonate, trifluromethylsulfonylimide, and bis(trifluoromethylsulfonyl)imide salts and ionic liquids based on 1,8-diazabicyclo[5.4.0]undec-7-ene and 1,5-diazabicyclo[ 4.3.0]non-5-ene

An Efficient Strategy for the Synthesis of 1-(Trifluoromethylsulfonamido)propan-2-yl Esters and the Evaluation of Their Cytotoxic Activity

Development of Palladium-Catalyzed Decarboxylative Allylation of Electron-Deficient Sulfones: Method Development and Mechanistic Studies

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