Copper I trifluoromethanesulfonate

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... 

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). 

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... 

Enantioselective Cyclopropanation of Alkenes. Cationic Cu complexes of methylenebis(oxazolines) such as (1), which have been developed by Evans and co-workers, are remarkably efficient catalysts for the cyclopropanation of terminal alkenes with diazoacetates. The reaction of styrene with ethyl diazoacetate in the presence of 1 mol % of catalyst, generated in situ from Copper(I) Trifluoromethanesulfonate and ligand (1), affords the (rans -2-phenylcyclopropanecarboxylate in good yield and with 99% ee (eq 3). As with other catalysts, only moderate transicis selectivity is observed. Higher transicis selectivities can be obtained with more bulky esters such as 2,6-di-r-butyl-4-methylphenyl or dicyclohexylmethyl diazoacetate (94 6 and 95 5, respectively). The efficiency of this catalyst system is illustrated by the cyclopropanation of isobutene, which has been carried out on a 0.3 molar scale using 0.1 mol % of catalyst derived firom the (R,R)-enantiomer of ligand (1) (eq 4). The remarkable selectivity of >99% ee exceeds that of Aratani s catalyst which is used in this reaction on an industrial scale. 

In an atmosphere of argon, a solution of 13.5 g (88%, 94 mmol) of S.6b and 300 mg (11 mmol) of copper (I) trifluoromethanesulfonate benzene complex (CuOTf) in 120 mL of dry diethyl ether is irradiated in a Pyrex photoreactor with a water cooled quartz immersion well by a high-pressure mercury lamp (HPK 125 W, Fa. Philips). After the reaction is complete (monitored by GLC), the mixture is concentrated in vacuo and purified by column chromatography (cyclohexane/ethyl acetate 2 3) to give 10.5 g (64% from... 

ULLMANN REACTION Copper(I) trifluoromethanesulfonate. Diethylamino(trimethyl)-silane. Tris(triphenylphosphine)nickel(0). 

Until the end of the 1970 s, interest in such reactions concentrated on catalysis by copper salts (review Burke and Grieco, 1979), obviously influenced by the long, broad, and successful experience with copper +- and copper-ions in aromatic diazo chemistry (Sandmeyer, Pschorr and Meerwein reactions, see Zollinger, 1994, Chapts. 8 and 10). A landmark was the discovery of Salomon and Kochi (1973), who found that cyclopropanations with diazomethane in the presence of copper(i) trifluoromethanesulfonate (triflate OTf) resulted in reduction of Cu + to Cu +, and that the rate of dediazoniation is inversely proportional to the alkene concentration. These results strongly indicate that formation of an alkene-Cu+ complex (8-47 2) precedes the complex formation with the diazoalkane. 

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