Trifluoromethanesulfonyl fluoride

An example of cleavage ol the sulfur-oxygen bond in trifluoromethane-sulfonic ester has been reported Tnfluororaethyl triflate reacts with neutral or anionic nucleophiles with elimination of carbonyl difluoride and formation of trifluoromethanesulfonyl fluoride [57] (equation 32) The mechanism of this reaction involves elimination of fluoride ion, which is a chain carrier in the substitution of fluorine for the trifluoromethoxy group... 

The substitution of an inorganic ester group, such as /t-toluenesulfonate (tosylate), methanesul-l onate (mesylate), trifluoromethancsulfonate (triflate), cyclic sulfate, etc., by fluorine is one of the most important methods for the introduction of fluorine into aliphatic molecules. It is an indirect method for the substitution of a hydroxy group with a fluorine. By using an in situ esterification, e.g. with trifluoromethanesulfonyl fluoride, and fluorination, c.g. with tetrabutyl-ammonium fluoride, it also provides a one-pot reaction for realizing this reaction. 

Trifluoromethanesulfonyl fluoride, CF3S02F, is prepared by the electrolysis of CH3SO2CI in hydrogen fluoride. The higher perfluoroalkanesulfonyl fluor des are prepared similarly. This application of the electrolytic process of Simons (281, 282) was made independently by three parties (a) Brice and Trott, 1956 (29) (b) Gramstad and Haszeldine, 1956 (114) (e) Burdon et al., 1957 (86). 

Triflyl chloride was also used for the preparation of fluoroalkyl trifluoromethanesulfonates that act as highly efficient fluoroalky-lating reagents, 10 times more reactive than the corresponding tosylates. Significant formation of fluoroalkyl ether side-products was observed when trifluoromethanesulfonyl fluoride was used. Fluoroalkyl p-nitrophenyl ethers were thus prepared in high yields, without side-elimination reactions (eq 7). ... 

Lately Garg and Shreeve suggested a simple synthesis of trifluoromethanesul-fonamide derivatives of 3-amino- and 3,5-diamino-l,2,4-triazoles 88, 89 from the corresponding aminoazoles and trifluoromethanesulfonyl fluoride [86],... 

Fluorination of trifluoromethanesulfonyl carbohydrates with cesium fluoride under forcing conditions (130 °C in dimethylformamide) [55] or the use of acetyl protected substrates [56] gives considerably lower yields... 

GABA HMG-CoA HMPA HT LDA LHMDS LTMP NADH NBH NBS NCS NIS NK NMP PMB PPA RaNi Red-Al RNA SEM SnAt TBAF TBDMS TBS Tf TFA TFP THF TIPS TMEDA TMG TMP TMS Tol-BINAP TTF y-aminobutyric acid hydroxymethylglutaryl coenzyme A hexamethylphosphoric triamide hydroxytryptamine (serotonin) lithium diisopropylamide lithium hexamethyldisilazane lithium 2,2,6,6-tetramethylpiperidine reduced nicotinamide adenine dinucleotide l,3-dibromo-5,5-dimethylhydantoin A-bromosuccinimide A-chlorosuccinimide A-iodosuccinimide neurokinin 1 -methyl-2-pyrrolidinone para-methoxybenzyl polyphosphoric acid Raney Nickel sodium bis(2-methoxyethoxy)aluminum hydride ribonucleic acid 2-(trimethylsilyl)ethoxymethyl nucleophilic substitution on an aromatic ring tetrabutylammonium fluoride tert-butyldimcthyisilyl fert-butyldimethylsilyl trifluoromethanesulfonyl (triflyl) trifluoroacetic acid tri-o-furylphosphine tetrahydrofuran triisopropylsilyl A, N,N ,N -tetramethy lethylenediamine tetramethyl guanidine tetramethylpiperidine trimethylsilyl 2,2 -bis(di-p-tolylphosphino)-l,r-binaphthyl tetrathiafulvalene... 

Ammonium fluoride itself is not widely used, however, sporadic reference to it exists.187 Tetramethylammonium fluoride gives very good yields of the fluoro derivative 2 on reaction with l,6-anhydro-3,4-di-0-benzyl-2-0-(trifluoromethanesulfonyl)-/l-D-mannopyranose (1) in... 

NMO NMP Nu PPA PCC PDC phen Phth PPE PPTS Red-Al SEM Sia2BH TAS TBAF TBDMS TBDMS-C1 TBHP TCE TCNE TES Tf TFA TFAA THF THP TIPBS-C1 TIPS-C1 TMEDA TMS TMS-C1 TMS-CN Tol TosMIC TPP Tr Ts TTFA TTN N-methylmorpholine N-oxide jV-methyl-2-pyrrolidone nucleophile polyphosphoric acid pyridinium chlorochromate pyridinium dichromate 1,10-phenanthroline phthaloyl polyphosphate ester pyridinium p-toluenesulfonate sodium bis(methoxyethoxy)aluminum dihydride (3-trimethylsilylethoxy methyl disiamylborane tris(diethylamino)sulfonium tetra-n-butylammonium fluoride f-butyldimethylsilyl f-butyldimethylsilyl chloride f-butyl hydroperoxide 2,2,2-trichloroethanol tetracyanoethylene triethylsilyl triflyl (trifluoromethanesulfonyl) trifluoroacetic acid trifluoroacetic anhydride tetrahydrofuran tetrahydropyranyl 2,4,6-triisopropylbenzenesulfonyl chloride 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane tetramethylethylenediamine [ 1,2-bis(dimethylamino)ethane] trimethylsilyl trimethylsilyl chloride trimethylsilyl cyanide tolyl tosylmethyl isocyanide meso-tetraphenylporphyrin trityl (triphenylmethyl) tosyl (p-toluenesulfonyl) thallium trifluoroacetate thallium(III) nitrate... 

Scheme 12.10. Synthesis of a-onocerin using butyldimethylsilyl, THF = tetrahydrofuran, a three-component nucleophilic addition/Brook Tf = trifluoromethanesulfonyl, DME = 1,2-rearrangement/alkylation on acylsilanes, by dimethoxyethane, TMS = trimethylsilyl, Corey and co-workers [33]. TBS = t- TBAF = n-tetrabutylammonium fluoride.

TASF tris(diethylamino)sulfonium difluoro(trimethyl)silicate TBAF tetrabutylammonium fluoride Tf trifluoromethanesulfonyl THF tetrahydrofuran tol tolyl... 

Due to these safety problems, the search for new, easy-to-handle electrophilic fluorinating agents has become an important area of research. Some of these new reagents have been tested in the fluorination of enamines to give a-fluoro ketones. These include l-fluoropyridin-2(l//)-one (9), A -fiuoroquinuclidinium fluoride (NFQNF, 10), Af-fluoropyridinium salts 11, and A -fluorobis(trifluoromethanesulfonyl)aminc (Tf2NF. 12). ... 

Other aryl fluoroalkanesulfonates besides trifluoromethanesulfonyl esters of phenols can be reduced to arenes. Moreover, the preparation of such esters and their reduction may be carried out in one pot . A mixture of m-methoxyphenol, perfluorooctanesulfonyl fluoride, triethylamine, dimethylformamide, for-... 

Abbreviations Ac acetyl AIBN azobisisobutyronitrile All allyl Bn benzyl Bz benzoyl ClAc chloroacetyl DAST diethylaminosulfur trifluoride DBU l,8-diazabicyclo[5.4.0]-undec-7-ene DDQ 2,3-dichloro-5,6-dicyano-/)-benzoquinone DMDO dimethyldioxirane DMTST dimethyl(methylthio)sulfonium trifluoromethanesulfonate Fmoc 9-fluorenyl-methoxycarbonyl HDTC hydrazine dithiocarboxylate IDCP iodonium di-collidine perchlorate Lev levulinoyl MBz 4-methylbenzoyl Me methyl MEK methyl ethyl ketone MP 4-methoxyphenyl NBS iV-bromosuccinimide NIS A-iodosuccinimide Pent n-pentenyl Pfp pentafluorophenyl Ph phenyl Phth phthaloyl Piv pivaloyl PMB 4-methoxybenzyl TBAF tetrabutylammonium fluoride TBDMS tcrt-butyldimethylsilyl TBDPS tert-butyldiphenylsilyl TCA trichloroacetyl TES triethylsilyl Tf trifluoromethanesulfonyl TMS trimethylsilyl Tol 4-methylphenyl Tr trityl Troc 2,2,2-trichloroethoxycarbonyl Ts tosyl. 

A second type of ligand coupling reaction of vinylstannane was reported by Tins and Kawakami. The reaction of vinylstannanes with in situ generated trifluoromethanesulfonyl hypofluorite leads to vinyl fluoride according to the mechanism depicted in scheme 8.3. 

A comprehensive review of the different approaches for [ F]FDG production has been published by Fowler and Ido (2002) (cf. O Table 42.8). [ F]FDG is produced nowadays by a two-step process developed by Hamacher et al. (1986a) (O Fig. 42.16). The procedure consists of a nucleophilic aliphatic substitution of tetra-acetyl-trifluoromethanesulfonyl-P-D-mannopyranose (tetraacetylated mannosyl-2-triflate) by F-fluoride-for-triflate exchange with [K/2.2.2] F in acetonitrile (up to 95% incorporation of F-fluoride). 

The most conunon application of oxygen-functionalized ILs is as electrolytes for litMum batteries due to their low viscosities, high conductivities, and reasonably high electrochemical stability [53, 56, 57, 73, 74]. The Quartarone group [75] prepared composite electrolytes based on PVdF-HFP [poly(vinylidene fluoride-co-hexafluoropropene)] gelled with a 0.41 mol/kg solution of Li[N(T02] in A-methoxyethyl-A-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide when... 

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