Trifluoromethanesulfonic imide

Katayama Y, Morita T, Yamagata M et al (2003) Electrodeposition of metaUic lithium on a tungsten electrode in 1-butyl-l-methylpyrroUdinium bis(trifluoromethanesulfone)imide room-temperature molten salt. Electrochemistry 71 1033-1039... 

In 2004, Ding et al. synthesized the chiral ILs (lS,2P)-(- -)-N,N-dimethylephedrinium-bis(trifluoromethanesulfon) imidate, (lJt,2S)-(-)-dimethylephedrinium-bis(trifluoromethanesulfon) imidate, and racemic (1S,2S)-(-F)-N,N-dimethyIpseudoephedrinium-bis(trifluoromethanesuIfon) imidate for coating of fused-silica capillary tubes (250 pm inner diameter, polyimide coated) [42], All ILs showed enantioselective retention for at least four general classes of... 

We observed that whatever reactants addition order is, we only obtained the expected product, with a yield of 85% when we use bis(trifluoromethanesulfone)imide acid (HNTf2). With HBF4 and HPFe, when NMI and acrylic acid react first, acrylic acid plays the role of an... 

Fig. 2 The chromatograms of enantioseparation using (/ )-MA, iV-trimethyl-2-aminobutanol-bis(trifluoromethanesulfon)imidate CIL 5 as chiral selector, (a) propranolol in HPCE, 10 mmol/L CIL 5 voltage, 16 kV, with anodic detection at 254 nm (b) enantioseparation of 2,2 -diamino-l,r-binaphthalene in HPLC eluent H2O-CH3CN (6 4, v/v) containing 10 mmol/L of chiral selector 5, detection, 254 nm (c) enantioseparation of citronellain GC on 5, split ratio 80 1, FID. Adapted from [76]...

The CIL, (7 )-/V,/V,/V-trimethyl-2-aminobutanol-bis(trifluoromethanesulfon) imide (5), was also found to be a good chiral selector for a variety of compounds in GC (Fig. 2). For instance, this CIL afforded good resolution in the enantioseparation of citronellal (Fig. 2C) [76],... 

A highly Lewis acidic silyltriflimide can be generated in situ upon treatment of silyl enol ethers with bis(trifluoromethanesulfon)imide (Tf2NH) in a catalytic amount. For example, enol tris(trimethylsilyl)silyl ethers derived from aldehydes react with another aldehyde in the presence of a catalytic amount of TfjNH to give cross-aldols exclusively (Scheme 3-80). ... 

Trichloroacetonitrile reacts with glycosidic hydroxy groups of protected sugars to form glycosyl trichloroacetimidates (R. R. Schmidt, 1980, 1984,1985,1986 B. Wegmann, 1988). The imidate is substituted by alcohols in the presence of trimethylsilyl trifluoromethanesulfonate... 

RTILs consist of large, unsymmetrical ions, such as 1,3-dialkyl-imidazolium, 1-alkylpyridinium, 1-alkylpyrazolium, tetralkylammonium or tetralkyl-phosphonium cations and tetrachloroaluminate, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate or bis((trifluoromethyl) sulfonyl)imide anions. 

Thus, the best compromises for Boc and Fmoc chemistries seem to be cyclohexyl and 2,4-dimethylpent-3-yl (Dmpn), which is of intermediate stability, and the removal of which by trifluoromethanesulfonic acid with the aid of thioanisole (see Section 6.22) leads to minimal imide formation (see Section 6.13). Points to note are that acidolysis of esters by hydrogen fluoride can lead to fission at the oxy-car-bonyl bond instead of the alkyl-oxy bond, thus generating acylium ions that can react with nucleophiles (see Sections 6.16 and 6.22), and that benzyl esters may undergo transesterification if left in methanol. The side reactions of cyclization (see Section 6.16) and acylation of anisole (see Section 6.22) caused by acylium ion formation do not occur at the side chain of aspartic acid.47-51... 

PEPTIDES Bis(o-nitrophenyl)phenyl-phosphonate. Dicyclohexylcarbodi-imide. Diphenyl N-succinimidyl phosphate. N-Methyl-N-phenylbenzohydra-zonyl bromide. n-Propylphosphonic anhydride. Trifluoromethanesulfonic acid-Thioanisole. 

AcOOH, KBr, AcOH, NaOAc, 1.5h, 20°C, 82-92% yield. The SMOM group is stable to B114NF NaOMe/MeOH 4 N NaOH/dioxane/methanol A/-iodosuccin-imide, cat. trifluoromethanesulfonic acid. 

Trimerization of nitriles, isocyanates, isothiocyanates, imidates, and carbodiimides all lead to symmetrical 2,4,6-trisubstituted 1,3,5-triazines (see Section 6.12.9.5). The use of lanthanide trifluoromethanesulfonate and ammonia as cocatalysts is claimed as a big improvement. The trisaminal of 2,4,6-triformyl-l,3,5-triazine is also useful for further derivatization to unusual structures (see Section 6.12.7.1). Treatment of a 1 1 pyridine/conc. ammonia solution of an aromatic aldehyde with excess Fremy s salt is another development. Separation of the amide coproduct was claimed to be easy. The synthesis fails with aliphatic aldehydes (see Section 6.12.9.5.4). Aminolysis of 2,4,6-triaryl-1,3,5-oxadiazinium salts gives symmetrical 1,3,5-triazines but the reactions are limited in that electron-withdrawing groups in the aromatic rings lead to instability and difficulty in separation of products (see Section 6.12.10.4). 

Benzyl 2.2,2-trichloroacetimidate (bp 106-114 00.07 kPa) alkylates alcohols in the presence of trifluoromethanesulfonic acid. Esters, imides, isopropylidene and benzylidene acetals are unaffected. This method allows the formation of benzyl ethers in molecules that are base-sensitive. In the example [Scheme 4.167],2 benzylation of the p-hydroxy ester 167.L1 under the usual basic conditions would lead to retro-aldol reactions and/or elimination. A synthesis of the cellular messenger L-a-phosphatidyl-D-/nyo-inositol 3,4-bisphosphate exemplifies the use of trityl cation-promoted benzylation of two adjacent hydroxyls [Scheme 4.168]. ... 

R. Y. Garlyauskayte, A. N. Chemega, C. Michot, M. Armand, Y. L. Yagupolskii, L. M. Yagupolskii, Org. Biomol. Chem. 2005, 3, 2239-2243. Synthesis of new organic super acids—V-(trifluoromethylsulfonyl)imino derivatives of trifluoromethanesulfonic acid and bis(trifluoromethylsulfonyl)imide. 

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