Sulfonimides

Br0S02F has also been used to prepare new N-bromo sulfonimides such as (CF3S02)2NBr. Other novel compounds include [I(0S02F)2] -j-(i58) mixed valent iodine (III,V) poly-... 

The interfacial properties of gel electrolytes containing ethylene carbonate immobilized in a polyacrylonitrile (PAN) matrix with a lithium (bis)trifluoromethane sulfonimide (LiTFSI) salt have been studied 1139]. SEI stability appeared to be strongly dependent on the LiTFSI concentration. A minimum value of / SE1 of about 1000 Qcm2 was obtained after 200h... 

Ahnlich werden Chinon-bis-sulfonimide durch Lithiumalanat zu Bis-sulfonamiden reduziert2. 

When the C=N bond is fixed in a ring system in which no (E)/(Z) isomerization can take place, the asymmetric hydrogenation of the C=N bond can be highly enantioselective. Oppolzer et al." found that cyclic sulfonimide was hydrogenated with an Ru(BINAP) catalyst to give a product with essentially quantitative optical yield (Scheme 6-45). 

Chalkova, E., Zhou, X., Ambler, C., Hofmann, M. A., Weston, J. A., Allcock, H. R. and Lvov, S. N. 2002. Sulfonimide polyphosphazene-based H2/O2 fuel cells. Electrochemical and Solid-State letters 5 A221-A222. 

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... 

Figure 44. Synthesis of a sulfonimide containing an activiated dichloro monomer.

The presence of a heteroatom directly connected to the nitrogen atom of the imine activates it toward hydrogenation, while creating a second coordination site for the catalyst. Indeed, some successful results have been achieved for the hydrogenation of N-acylhydrazone, sulfonimide, and N-diphenylphosphinyl ketimines. The Et-DuPhos-Rh complex is an efficient catalyst for the asymmetric hydrogenation of a variety of N-acyl- ... 

The asymmetric fluorination of enolates by means of chiral metal complexes has been reported with Selectfluor in the presence of a chiral Lewis acid derived from TADDOL (TiCl2/TADDOL), or with F-A-sulfonimide (NFSI) with palladium complexes and chiral phosphines. 

The fluorination of enolates of ketone, amide, or hydrazone bearing a chiral auxiliary (SAMP, Evans oxazolidine) with nonchiral fluorination reagent (A-fluoro sulfonimides, A-fluoropyridine) occurs with excellent diastereoselectivities. ... 

The electrophilic fluorination of chiral bicyclic lactams (prepared from the epimers of pyroglutamic acid) by means of A-fluoro sulfonimide (NFSI) yields l- and d-4, 4-difluoroglutamic acids and 4,4-difluoroglutamines (Figure 5.21). They have also been prepared with a good ee starting from ethyl (/ )-bromodifluoroalaninate. ... 

Polyphosphazenes block copolymers containing sulfonimide side groups, (V), were prepared by Allcock et al. (4) and used in membrane blends in fuel cells. 

BINAP-Ru(II) complex can hydrogenate a special cyclic sulfonimide in 84% yield to the sultam, which is used as a chiral auxiliary, with greater than 99% ee (Scheme 77) (116). 1... 

A RhCp complex (S,S)-6 (Cp =pentamethylcyclopentadienyl), which is iso-lobal with Ru(rj6-arene) complex (S,S)-5 (Scheme 13), effected the transfer hydrogenation of a cyclic imine substituted by an isopropyl group with an S/C of 200 in the presence of a 5 2 mixture of formic acid and triethylamine to give the R amine in 99% ee (Scheme 13) [31]. When the reaction was performed with an S/C of 1,000, the optical yield decreased to 93%. The methyl imine was reduced with a 91% optical yield. Reduction of a cyclic sulfonimide resulted in the R sul-tam in 81% ee. 

Similarly, spirotriazoline intermediates from the addition of p-nitrobenzenesulfonyl azide to exocyclic olefins 22 and 23 give a single ring-expanded sulfonimide (97),18 7 190-19 2 whereas those derived from 24 yield two sulfonimides, 97 from ring expansion and 98 from methyl migration.187 Four... 

Three examples of polyphosphazenes that function as proton conductors are shown in 3.80-3.82.181 185 All three are aryloxyphosphazenes with acidic functional groups on the aryl rings. Their performance in operating fuel cells is comparable to that of Nation, but they are much more resistant to methanol crossover. The sulfonimide derivative (3.82) functions as a proton conductor at higher temperatures than Nation, and this is an advantage for future developments. 

A more widely applicable method is reaction of dried diazonium o-benzenedi-sulfonimides with sulfur nucleophiles in methanol solution, caution is still advised... 

The cyclic sulfonimidate 132 reacts readily with carbon nucleophiles, for example, methyllithium, to afford the methylsulfoximine 133 which can be deprotonated by an excess of lithium hexamethyldisilazide (LHMDS) and reacted with a second equivalent of the sulfonimidate yielding the bis(sulfoximine) 134 in a one-pot sequence with 62% yield (Scheme 20) <2004ASC1295>. 

Separation of C02 from N2 or CH4 comprises an area of critical industrial, social, and environmental importance where room-temperature ionic liquids (RTILs) are showing great potential [3, 63, 64], The commonly used ILs for this purpose are l-alkyl-3-methylimidazolium salts, represented by the formula [C MIm][X, where C is an n-alkyl chain of varying length and X is typically a molecular anion with a delocalized negative charge, such as bis(trifluorome-thane)sulfonimide, [Tf2N ] (Scheme 4.4) [65-71]. 

The sulfonimide (238) has been copolymerized with CH2=CHCN and CH2=C(Me)C02Me to produce a useful fibre (75GEP2346566), and the bis(oxathiazolone) (239), as a nitrile sulfide precursor (Scheme 5), has been used in the vulcanization of SBR... 

When diaryl telluriums were oxidized with ter .-butyl hypochlorite and the oxidation products reacted with sodium sulfonamides, diaryl tellurium sulfonimides were obtained in quantitative yield2. 

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