I Trifluoromethanesulfonate

Anion Source for Palladium Catalysis. The reagent serves as a source of weakly coordinating anions in the palladium-catalyzed formation of mixed phenyl ureas, a known class of commercially available herbicides, using palladium(II) acetate, copper(II) toluenesulfonate, and 2,2 -dipyridyl as the catalyst system. Other studies have suggested that use of this reagent to form palladium salts may have useful applications in the reductive carbonylation of nitroaromatic compounds to give isocyanates via initial carbamate formation (eq 2).  

Related Reagents. Copper(II) Methanesulfonate Copper(II) Nitrobenzenesulfonate Thallium(III) Toluenesulfonate. Indirect a-Sulfonyloxylation has been achieved using Koser s reagent and related derivatives p-Nitrobenzenesulfonyl Peroxide other related reagents.  

Jeff D. McGilvra Viresh H. Rawal University of Chicago, Chicago, IL, USA 

Physical Data moisture-sensitive white crystalline solid. Solubility soluble in MeCN, AcOH, 2-butanone, alkenes slightly soluble in benzene. 

Form Supplied in commercially available or can be prepared. Better results are often obtained when freshly prepared (CuOTf)2-CeHe complex is used. 

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VINYL SULFIDES FROM TinOACETALS WITH COPPER(I) TRIFLUOROMETHANESULFONATE (Z)-2-METH0XY-1-PHENYLTHI0-13-BUTADIENE... 

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. ... 

Bis[copper(I) trifluoromethanesulfonate] benzene complex Copper, [ Lt-(benzene)]bis(trifluoromethanesulfonato-0)di- (9) (37234-97-2)... 

The procedure described above provides a sufficient quantity of bis[copper(I) trifluoromethanesulfonate] benzene complex for several reactions at the scale used in Part C. If bis[copper(I) trifluoromethanesulfonate] benzene complex for a single reaction is desired, the same procedure can be followed at the appropriate scale without the use of the glove bag. In this case, the decolorized solution is not filtered but instead is cooled, and the product is allowed to crystallize in the reaction vessel. The supernatant benzene is decanted, and the crystals are washed in the flask with fresh benzene. The bis[copper(I) trifluoromethanesulfonate] benzene complex is then used without drying hj the same flask. 

Vinyl Sulfides from Thioacetals and Thioketals with Copper(I) Trifluoromethanesulfonate... 

Contact of this oxidant with readily oxidisable materials may lead to explosions. See Chlorine(I) trifluoromethanesulfonate... 

Simple olefins can photodimerize to cyclobutanes in the presence of cuprous salts as sensitizers (4.20) 423>. Copper (I) trifluoromethanesulfonate has been utilized successfully (4.21) 424). 

Reaction with trifluoromethanesulfonic anhydride in benzene yields cop-per(I) trifluoromethanesulfonate, [Cu(03SCF3)]2 CeHs, a white crystalline, air-sensitive complex (Cotton, F. A., G. Wilkinson, C. A. Murillo and M. Bochmann. 1999. Advanced Inorganic Chemistry, 6th ed. pp. 857-858. New York Wiley Interscience) Olefins can displace benzene in the above compound readily, forming a variety of olefin complexes. 

If one of the C —C double bonds of the 1,6-diene is incorporated in or attached to a ring (e.g., cycloalkene, methylenecycloalkane) tricyclic compounds containing a bicyclo[3.2.0]heptane subunit are obtained as products. Thus, photobicyclization of monocyclic diallyl ethers or homoallyl vinyl ethers afford oxatricycloalkanes.6 Similarly, allylic alcohols containing an additional cycloalkenyl ring are converted to oxatricycloalkanes by irradiation in the presence of copper(I) trifluoromethanesulfonate as catalyst.9... 

TRIS(l,2-BIS(DIMETHYLPHOSPHINO)ETHANE)-RHENIUM(I) TRIFLUOROMETHANESULFONATE, [Re(DMPE)3] [CF3SO3] ... 

A. PREPARATION OF TRIS(l,2-BIS(DIMETHYLPHOSPHINO)-ETHANE)RHENIUM(I) TRIFLUOROMETHANESULFONATE FROM DIOXOTETRAKIS(PYRIDINE)RHENIUM(V) TRIFLUOROMETHANESULFONATE... 

Tris(l,2-bis(dimethylphosphino)ethane)rhenium(I) trifluoromethanesulfonate is a white solid which can be oxidized to the purple Re(II) analog. This Re(I) salt is soluble in methanol, ethanol, dichloromethane, acetone, dimethyl sulfoxide (DMSO), and acetonitrile, and insoluble in diethyl ether [N.B. This Re(I) complex is unstable in nitromethane, presumably suffering oxidation to Re(II)]. 

Glycosidation Allyl chloroformate, 9 Boron trifluoride etherate, 43 Silver(I) tetrafluoroborate, 273 Silver (I) trifluoromethanesulfonate, 274 Thallium zeolites, 296 Tin(II) trifluoromethanesulfonate, 301 Trichloroacetonitrile, 321 Grignard reactions and reactions of... 

E)-(Carboxyvinyl)trimethylam-monium betaine, 67 Ethyl 3,3-diethoxyacrylate, 131 Potassium hydride, 257 aza-Claisen rearrangement L-Valinol, 341 Cope rearrangement Ferric chloride, 133 oxy-Cope rearrangement Potassium hydride, 257 Silver(I) trifluoromethanesulfonate, 274... 

Trichloroacetonitrile, 321 C-Glycosides Allyltrimethylsilane, 11 Organoaluminum reagents, 202 Silver(I) trifluoromethanesulfonate,... 

The synthesis of chlorine (I) and bromine (I) trifluoromethanesulfonates (triflates) was reported by DesMarteau. Stability and reactivity of these materials are similar to those of perfluoroalkyl hypohalites. Both compounds readily react at low temperature with a variety of fluoroolefins. Based on NMR analysis of the products of adding CF3S020X to pure cis- or trans-isomers of 1, 2-difluoroethylene, it was concluded that the reaction proceeds as syn-addition [35]. This statement was later criticized [18], since the assignment of stereoisomers was found to be incorrect. According to [18], addition of CF3S020X to haloolefins, as well as reactions of ClF, BrF and IF proceed as anti-addition via cyclic halonium cationic intermediates. 

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