Copper® trifluoromethanesulfonate

Vinyl Sulfides from Thioacetals with Copper Trifluoromethanesulfonate ... 

Besides the l-(but-3-enyl)allyl alcohols discussed above, 2- and 3-(pent-4-enyl)allyl alcohols also undergo clean photobicyclization in the presence of copper trifluoromethanesulfonate as catalyst. However, no intramolecular photocycloaddition product could be isolated from irradiation of a homologous 2-(hex-5-enyl)allyl alcohol.8... 

SENSITIZERS AP = acetophenone BP = benzophenone A = acetone B = methyl 3,5-bis(trifluoromethyl)benzoate C = (-)-tetrabomyl 1,2,4,5-benzene tetracarboxylate D = (-)-hexakis(l-methylheptyl) benzenehexacarboxylate MB = methyl benzoate P = phenan-threne CNN = 1-cyanonaphthalene DCA = 9,10-dicyanoanthracene DCB = 1,4-dicyano-benzene DCN = 1,4-dicyanonaphthalene CuOTf = copper trifluoromethanesulfonate benzene complex TPT = tetraphenylpyrylium tetrafluoroborat. 

Further studies carried out on methyl artemisinate (278) confirm that the hydroperoxide (279) rearranges to the enol (280) which is subsequently autoxidized to (281) and thence to artemisitene (282) under catalysis with acid or copper trifluoromethanesulfonate (Scheme 41) <95JA11098>. It is likely that (279) rearranges by homolysis to the 1,4-diradical (283) which then cleaves to (280). In... 

Decomposition of the diazoacetic ester (548) to the keto carbene (549) is promoted by copper(II) trifluoromethanesulfonate. In the presence of nitriles, 1,3-dipolar addition to the nitrile occurred giving the oxazole (550) (75JOM(88)ll5) (see also Section 4.03.8.1). 

The original Sonogashira reaction uses copper(l) iodide as a co-catalyst, which converts the alkyne in situ into a copper acetylide. In a subsequent transmeta-lation reaction, the copper is replaced by the palladium complex. The reaction mechanism, with respect to the catalytic cycle, largely corresponds to the Heck reaction.Besides the usual aryl and vinyl halides, i.e. bromides and iodides, trifluoromethanesulfonates (triflates) may be employed. The Sonogashira reaction is well-suited for the synthesis of unsymmetrical bis-2xy ethynes, e.g. 23, which can be prepared as outlined in the following scheme, in a one-pot reaction by applying the so-called sila-Sonogashira reaction ... 

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)... 

CHROMIUM TRIOXIDE-PYRIDINE COMPLEX, preparation in situ, 55, 84 Chrysene, 58,15, 16 fzans-Cinnamaldehyde, 57, 85 Cinnamaldehyde dimethylacetal, 57, 84 Cinnamyl alcohol, 56,105 58, 9 2-Cinnamylthio-2-thiazoline, 56, 82 Citric acid, 58,43 Citronellal, 58, 107, 112 Cleavage of methyl ethers with iodotri-methylsilane, 59, 35 Cobalt(II) acetylacetonate, 57, 13 Conjugate addition of aryl aldehydes, 59, 53 Copper (I) bromide, 58, 52, 54, 56 59,123 COPPER CATALYZED ARYLATION OF /3-DlCARBONYL COMPOUNDS, 58, 52 Copper (I) chloride, 57, 34 Copper (II) chloride, 56, 10 Copper(I) iodide, 55, 105, 123, 124 Copper(I) oxide, 59, 206 Copper(ll) oxide, 56, 10 Copper salts of carboxylic acids, 59, 127 Copper(l) thiophenoxide, 55, 123 59, 210 Copper(l) trifluoromethanesulfonate, 59, 202... 

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. 

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). 

An easy synthesis of the 2-oxo-2,3-dihydro-l/7-pyrrolo[l,2- ]pyrazole system can be performed by reaction of 1,2-diaza-1,3-butadienes 33 with dialkyl 1,3-acetonedicarboxylate 34 in the presence of potassium carbonate. At first, 1-aminopyrroles 36 was produced by dehydration in the presence of copper(n) trifluoromethanesulfonate. Treatment of these compounds with sodium hydride led to ATZ-substituted 2-oxo-2,3-dihydro-17/-pyrrolo[l,2-A]pyrazole 38. Under the same reaction conditions, and after acidic treatment, NH-BOC-protected 1-aminopyrrole was transformed to NH-unsubstituted 2-oxo-2,3-dihydro-l//-pyrrolo[l,2-A]pyrazole 37 (BOC =/-butylcarbonyl) (Scheme 1). 

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... 

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