Trifluoromethanesulfonamide

Trifluoromethanesulfonic acid anhydride, bp 84°C, is prepared by refluxing the acid over an excess of phosphorous pentoxide (18,26). The anhydride reacts instantaneously with ammonia or amines to form trifluoromethanesulfonamides. The anhydride reacts with most polar organic solvents. 

It was found, furthermore, that the substituent on the sulfonamide group of the chiral hgand strongly influenced the enantiofacial selectivity. Hence, ligand 81 bearing a tosyl substituent delivered the endo-(2il)-cycloadduct, whereas a trifluoromethanesulfonamide group afforded its enantiomer. The authors proposed that the latter substituent should increase the Lewis acid-... 

The use of chiral C2-symmetric trifluoromethanesulfonamides derived from (i )-1,1 -binaphthyl-2,2 -diamine in similar reactions to those described above has led to the formation of the expected alcohols with enantioselectivities of 43-54% ees. Better enantioselectivities were observed by Paquette et al, resulting from the use of chiral C2-symmetric VERDI (verbenone dimers) disulfonamides derived from the dimerisation of (+ )-verbenone. Stereoselectivity levels ranging from 72 to 98% ee were observed, depending on the structural characteristics of the aldehyde (Scheme 3.45). ... 

Scheme 3.53 Bis-(/ ,if)-trifluoromethanesulfonamide ligand for addition of ZnMe2 to a dialdehyde-Fe(CO)3 complex.

The to-trifluoromethanesulfonamide of frans-cyclohexane- 1,2-diamine also leads to enantioselective additions in 80% or greater e.e.158... 

Cho et al. have recently described the synthesis of a sulfonimide containing monomer and the resulting poly (ary lene ether sulfone) copolymers. In this procedure 3,3 -disulfonate-4,4 —dichlorodiphenyl sulfone was refluxed in thionyl chloride, isolated, and then reacted with trifluoromethanesulfonamide in the presence of triethylamine to form the sulfonamide analogue monomer as shown in Figure 44. This... 

On three occasions explosive products, not conclusively identified, were obtained when preparing this by fluorination of the lithium salt of trifluoromethanesulfonamide. 

N-nitroso-N-trifluoromethyl trifluoromethanesulfonamide [78], photolysis of bis-(trifluoromethyl)tellurium [79], thermal AIBN-induced decomposition of bis-(trifluoromethyl)mercury [80], thermolysis of highly branched perfluoro-carbons [81], and even thermolysis of persistent perfluoroalkyl radicals such as that discovered by Scherer [39, 45]. Recently it has even been found that per-fluorocarbons can be a source of perfluoroalkyl radicals when they undergo photoinduced reduction by NH3 or by Cp2TiF2 [82,83]. 

Sulfonyl groups can also be utilized to reduce the basicity of amino functions. Inter- and intra-molecu-lar cyclizadon using bifunctional tosylamides have been widely utilized in the preparation of macrocy-clic polyamines (Scheme 13). Trifluoromethanesulfonamide and its derivatives can also be used in the preparation of primary and secondary amines. ... 

In contrast to the anion of diethyl phosphoramidate or trifluoromethanesulfonamide, which cannot be cleanly monoalkylated, - the anion of trifluoroacetamide (100) was monoalkylated by alkyl halides or alkyl methanesulfonate. The resulting A -alkylamides (101) were converted into primary amines by alkaline hydrolysis or reduction (NuBHa Scheme 42). Various primary amines were prepared from (100) with primary alkyl iodides or methanesulfonate, benzyl and allyl halides, a-bromocarbonyl compounds and 2,4-dinitrochlorobenzene. However, competitive elimination is a serious side reaction for less reactive primary alkyl chlorides and secondary halides or methanesulfonate. The synthesis of secondary amines from (100) has also been reported. ... 

The silver salt of trifluoromethanesulfonamide, CFjSOjNAgj, reacts with phosgene in a sealed tube at 80 C to give the pseudohalide CFjSOjNCO and silver(I) chloride [154]. 

Aromatic sulfonic acid and perfluoroalkanesulfonic acids resins are widely used as ion-exchange resins in water treatment and multiple other industrial applications. In the form of membranes, they are routinely used in electrochemical cells, particularly in electroplating of metals and in battery applications. The lithium salts of trifluoromethanesulfonic acid and N-trifluoromethanesulfonyl trifluoromethanesulfonamide are both employed as electrolytes in secondary battery applications. 

A trifluoromethanesulfonamide can be prepared from a primary amine to allow monoalkylation of that amine. The triflamide is not stable to strong base, which causes elimination to an imine, but when used to protect an indole, it is cleaved with K2CO3 in refluxing methanol. ... 

Like the trifluoromethanesulfonamides, phenacylsulfonatnides are used to prevent dialkylation of primary amines. Phenacylsulfonamides are prepared in 91-94% yield from the sulfonyl chloride, and they are cleaved in 66-77% yield by Zn/AcOH/ trace HCl. ... 

Best, J. D. et al., In vivo characterization of Abeta(40) changes in brain and cerebrospinal fluid using the novel gamma-secretase inhibitor N-[cis-4-[(4-chlorophenyl)sulfonyl]-4-(2,5-difluorophenyl)cyclohexyl]-l,l,l-trifluoromethanesulfonamide (MRK-560) in the rat, J. Pharmacol. Exp. Ther., 317(2), 786, 2006. 

After formation of the acylimine (12), methanol adds to the less sterically hindered CC-face of the molecule with high selectivity to provide (13). A further direct incorporation of a 6cc-methoxy group (41) and subsequendy a 6a-formamido group into penicillin has been achieved using trifluoromethanesulfonamides of type (14) (42). 

S)-Pyrrolidine trifluoromethanesulfonamide 3a is a highly active catalyst for the asymmetric conjugate addition of aldehydes and ketones to nitroalkenes. The use of catalyst 3a (20 mol%) in i-PrOH at 0 °C, afforded a,a-dialkyl aldehydes with good to high yields and high to excellent levels of diastereo- and enantioselectivity (Scheme 9.20). In addition, the reactions of various cyclic and acyclic ketones with aromatic nitro-olefins indicated the usefulness of the catalyst. " Computational results corresponded with the observed stereoselectivities of 3a-catalysed Michael reactions. 

Phenyl sulfone. See Diphenyl sulfone Phenylsulfonic acid. See Benzenesulfonic acid Phenyl sulfonyl hydrazide Phenyl sulfonyl hydrazine. See Benzenesulfonyl hydrazide N-(4-Phenylsulfonyl-o-tolyl)-1,1,1-trifluoromethanesulfonamide. See Perfluidone Phenyl-(3-sulfopropyl) ether, potassium salt CAS 89574-82-3 Empirical C9H11KO4S Uses Intermediate for dyes Trade Name Synonyms PSP [Raschig AG http //www. raschig. de]... 

In the case of Brpnsted acid-mediated glycosyl fluoride donor glycosylations, the effect of counter-ion was also found to be as important as that of solvent [21]. For instance, trifluoromethanesulfonic acid favoured the formation of the a-glycoside, whereas bis-trifluoromethanesulfonamide favoured p. Interestingly, this phenomenon was emphasised by the demonstration of matched and mismatched selectivities... 

In 2007, a SILP-SCCO2 system was first applied to a continuous-flow process by Hintermair et al. [53]. They reported the continuous-flow hydroformylation of 1-octene (Figure 18.8) using a SILP catalyst where a rhodium complex was dissolved in [OMIM][NTf2] (l-octyl-3-mefhylimidazoliumbis(trifluoromethanesulfonamide)) supported on silica by adsorption. The system is shown schematically in Figure 18.8. 

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