2- phenyl trifluoromethanesulfonate

Phenanthren-9-ylmethyl)phenyl trifluoromethanesulfonate 164 undergoes a palladium-catalyzed cyclization via S-0 bond cleavage to afford 14/f-dibenzo[ ,f]xanthene in moderate yield (Equation 76) <2002T5927>. 

Treatment of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 171 with KF generates benzyne, which can then react with aromatic aldehydes to furnish 9-aryl-97/-xanthenes in moderate yield (Scheme 55). Electron-rich aromatic aldehydes are necessary to obtain high yields of the desired xanthenes <20040L4049>. 

A solution of phenyl trifluoromethanesulfonate (30.0 mg, 0.13 mmol) and n-tridecane (10.0 mg, 0.054 mmol) in either toluene (0.5 mL) or benzene (0.5 mL) was added to a 5-mL Schlenk tube containing Pd2(dba)3 (2.3 mg, 0.004 mmol) and 1 -[4-(5)-terf-butyl-2-oxazolin-2-yl]-2-(5)-(diphenylphosphino)ferrocene (3.96 mg, 0.008 mmol) under an atmosphere of nitrogen. To this was added 2,3-dihydrofuran (46.2 mg, 0.65 mmol) and base (0.39 mmol) (Table 5.5). The resulting solution was degassed by three freeze-thaw cycles at 0.01 mbar and left to stir under nitrogen at 80 °C for 14 days giving a red solution with precipitation of Base.HOTf. 

Ring expansion of keto aziridines to the 2,5-diaryloxazoles in the presence of dicyclohexyl carbodiimide and iodine has been reported. A tandem thia-Fries rearrangement of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate aryne precursors has been described (Scheme 76). ° ... 

GjHjiOjP 116-17-6) see Clodronate disodium (3/t,45)-3-(triisopropylsilyloxy)-4-phenyl-2-azetidinone (C nH2()N02Si 132127-31-2) see Docetaxel triisopropylsilyl trifluoromethanesulfonate (C ()H2 F303SSi 80522-42-5) see Tacrolimus... 

The reaction of crotonaldehyde and methyl vinyl ketone with thiophenol in the presence of anhydrous hydrogen chloride effects conjugate addition of thiophenol as well as acetal formation. The resulting j3-phenylthio thioacetals are converted to 1-phenylthio-and 2-phenylthio-1,3-butadiene, respectively, upon reaction with 2 equivalents of copper(I) trifluoromethanesulfonate (Table I). The copper(I)-induced heterolysis of carbon-sulfur bonds has also been used to effect pinacol-type rearrangements of bis(phenyl-thio)methyl carbinols. Thus the addition of bis(phenyl-thio)methyllithium to ketones and aldehydes followed by copper(I)-induced rearrangement results in a one-carbon ring expansion or chain-insertion transformation which gives a-phenylthio ketones. Monothioketals of 1,4-diketones are cyclized to 2,5-disubstituted furans by the action of copper(I) trifluoromethanesulfonate. ... 

The Schiff base derivatives 73 of the 3-hetaryl-substituted 4-amino-3-thiol-l,2,4-triazoles, on treatment with acetic anhydride, undergo cyclization to give the corresponding 3-substituted-5-acetyl-5,6-dihydro-6-phenyl[l,2,4]triazolo[3,4-7][l,3,4]thiadiazoles 76 (Equation 16) <1990IJB135>. Similar treatment of 4-(A-bcnzoylamino)-4,5-dihydro-l-methyl-3-mcthylthio-1 //-[ 1,2,4 triazolc-5-thione 77 leads to the [l,2,4]triazolo[3,4-4][l,3,4]thiadiazolium trifluoromethanesulfonate 78 (Equation 17) <1986LA1540>. 

Phenyl-3,3-dichloro-l-azetine (222) forms a 2 1 complex with silver tetrafluoroborate and 1 1 complexes with silver trifluoromethanesulfonate and with boron trifluoride. The dibromo analogue of (222) affords a similar 2 1 complex with silver tetrafluoroborate (79CB3914). 

A reactor was charged with 93.80% 4,4 -diphenylmethane diisocyanate, 6.20% 2,4 -diphenylmethane diisocyanate, and 3-methyl-1 -phenyl-3-phospholene-1 -oxide (6 ppm) as catalyst and then heated for 6 hours at 110°C. Trifluoromethanesulfonic acid (50 ppm) was then added to quench the reaction. The mixture was then cooled to 50°C and the product isolated having a 29.5% isocyanate content. 

OTf Pc pda Ph phen phenba triflate = trifluoromethanesulfonate phthalocyanato(2 -) 1,2-pheny lenediaminato(2 -) phenyl 1,10-phenanthroline NJV -l, 2-phenylenebis[2-acetyl-l -amino-1 -buten-3-onato( 1 -)]... 

Instead of perchlorates, trifluoromethanesulfonates (tnflates) can be used They are readily prepared and claimed to be safer than perchlorates [75] 18F Aryl fluorides have been prepared from p YC6H4N+(CH3)3CF3S03- (Y = COCeHs, CN, CHO, NO2, COCH3, CO2C2H5) by this alternative substrate Fluorodequatermzation can also be applied to the preparation of fluonnated heterocyclics such as 4 fluoro 6 phenyl 1,3 pyrimidine [76] (equation 15) and fluoropunnes [77]... 

Tetraalkylammonium tosylates [74] and trifluoromethanesulfonates [72] are also excellent electrolytes. Although tetraalkylammonium ions are favored as the cations for supporting electrolytes because of their wide potential range, other cations are sometimes used for special applications—for example, methyltri-phenyl phosphonium, whose tosylate is freely soluble in methylene chloride, and other fairly nonpolar solvents [74] or metal ions (lithium salts tend to have the best solubility in organic solvents) where undesirable reactions of the tetraalkylammonium ion might occur [13,75]. The properties of many electrolytes suitable for nonaqueous use have been surveyed [76]. 

High catalytic activities have been achieved by the PYRPHOS- [18], PPCP [20], BICHEP- [21], Et-DuPHOS-Rh [19] complexes among others, allowing the reaction with a substrate-to-catalyst molar ratios (S/C) as high as 50,000. With a [2.2]PHANEPHOS-Rh complex, the reaction proceeds even at -45°C [27], Supercritical carbon dioxide, a unique reaction medium, can be used in the DuPHOS and BPE-Rh-catalyzed hydrogenation [43], A highly lipophilic counteranion such as tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BARF) or trifluoromethanesulfonate is used to enhance the solubility of the cationic Rh complexes. Under the most suitable reaction conditions of 102 atm of carbon dioxide, 1 atm of hydrogen, and 22°C, a-amino acid derivatives are produced with up to 99.7% ee. 

Lewis superacids, such as SbF5, AsF5, PF5, TaF5, NbF5, BF3, tris(pentafluoro-phenyl) borane, boron tris(trifluoromethanesulfonate), and aprotic organic superacids developed by Vol pin and co-workers. 

The reaction of 6-methylene-l,3-dioxepanes 89 with trimethylsilyl trifluoromethanesulfonate in the presence of lithium diisopropylamide gave 4-formyltetrahydropyrans 90 as ring-contraction products in 29-77% yield. In the case of 4-phenyl-substituted substrate 89a, trimethylsilyl enol ether 91 was isolated as an intermediate (Scheme 17) <2005BCJ2209>. 

Okuma et al. <1998CL79, 2000BCJ155, 1999J(P 1)2997, 2005H(65)1553> published a series of papers describing reactions of various thioketones with benzyne generated from 2-trimethylsilylphenyl trifluoromethanesulfonate 96, phenyl[2-(trimethylsilyl)-phenyl]iodonium trifluoromethanesulfonate 97, or benzenediazonium-2-carboxylate 98, which led to the formation of benzothietes. Compounds 96-98 are good precursors of benzyne, but not in the... 

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