Copper I halides

Some prapargylic halides can be converted into haloallenes by treating them with copper[I) halide and lithium halide, preferably in THF as solvent. A catalytic amount of the copper salt, which forms a soluble complex with lithium halide, is... 

Organometallic compounds of copper were known for a long time before their versatil ity in synthetic organic chemistry was fully appreciated The most useful ones are the lithium dialkylcuprates which result when a copper(I) halide reacts with two equivalents of an alkyllithium in diethyl ether or tetrahydrofuran... 

Copper(I) halide-catalyzed coupling reactions of perfluoro Gngnard reagents with allyl and propargyl halides have been reported [256], The acetylenic copper compound may be an intermediate in these reactions. 

Perfluoroarylcopper compounds are usually prepared from the corresponding perfluoroaryllithium, -magnesium, or -cadmium reagents and copper(I) halides [257] (equation 175). 

The perfluoroalkylthio- and pentafluorophenylthiocopper compounds have been used for the introduction of the -SRj- and -SAtf group into molecules [264, 265, 266, 267] for increased biological activity Trifluoromethylthiocopper has been prepared via metathesis of AgSCFj with copper(I) halides [264] and the... 

In the reactions of 10.13a with alkali metal terr-butoxides cage expansion occurs to give the sixteen-atom cluster 10.15, in which two molecules of MO Bu (M = Na, K) are inserted into the dimeric structure. The cluster 10.13a also undergoes transmetallation reactions with coinage metals. For example, the reactions with silver(I) or copper(I) halides produces complexes in which three of the ions are replaced by Ag" or Cu" ions and a molecule of lithium halide is incorporated in the cluster. ... 

Copper(I) halide supramolecular networks linked by N-heterocyclic donor bridging ligands 98PAC2351. 

Aryl chlorides and bromides are prepared by reaction of an arenediazonium salt with the corresponding copper(I) halide, CuX, a process called the Sandmeyer reaction. Aryl iodides can be prepared by direct reaction with Nal without using a copper(T) salt. Yields generally fall between 60 and 80%. 

Primary, secondary, and tertiary aliphatic amines have been cleaved to give aldehydes, ketones, or carboxylic acids with aqueous bromine and with neutral permanganate. The other product of this reaction is the amine with one less alkyl group. In a different type of procedure, primary alkyl primary amines can be converted to ge/n-dihalides, RCH2NH2 —> RCHX2 (X =Br or Cl), by treatment with an alkyl nitrite and the anhydrous copper(I) halide. 

Stereoselective alkynylation of 61 and subsequent triflation gave 62, a good precursor for conversion to 63 with copper(I) halides in DMF (Scheme 4.16) [28]. 

These transmetalations may be performed not only with copper) I) halides in DMF [104], but also by using Me2CuLi-LiCN. This transmetalation has been used in the synthesis of prostaglandin derivatives (Scheme 2.51) [105]. 

Copper(i).—Halides and Cyanides.cation, [Me2N=CH2] , which has been reported previously by Eschenmoser (Symposium on Stereochemistry, Sheffield, 1970) is potentially useful in stabilizing low-valent metal complexes, and its reaction with Cu(CO)Cl has been examined. The results are outlined in Scheme 9. 

Also in the case of intennediate 374, a lithium-copper transmetallation with a copper(I) halide (bromide or chloride) allowed one to carry out the conjugate addition [to electrophilic olefins R CH = CH2Z (Z = COR, CO2R) giving compounds 381 in 31-76% yield], the acylation (with acyl chlorides yielding ketones 382 in 35-65% yield) and dimerization [using copper(II) chloride as the additive, to give compound 383 in 59% yield] processes ... 

Owing to their instability at room temperature, complexes of straight-chain mono-olefins with copper(I) halides and with silver nitrate have been characterised mainly by distribution studies in solution, and, in the... 

Preparation of 1,4-Pentadiyne by Copper(I)halide-Catalysed Reaction of Propargyl... 

A large number of binary AB compounds formed by elements of groups IIIA and VA or IIA and VIA (the so-called III-V and II-VI compounds) also fcrystallize in diamond-like structures. Among the I-VII compounds, copper (I) halides and Agl crystallize in this structure. Unlike in diamond, the bonds in such binary compounds are not entirely covalent because of the difference in electronegativity between the constituent atoms. This can be understood in terms of the fractional ionic character or ionicity of bonds in these crystals. 

Mono-olefins (un) react with solid copper(I) halides to form unstable complexes of the type [CuX(un)] (X = Cl, Br), which dissociate into their constituents above 0° (67, 138). Dienes (e.g., butadiene, isoprene, pipery-lene, bicyclo[2,2,l]hepta-2,5-diene, and cyclopolyolefins) form more stable complexes of the type [Cu2X2(diene)J (1,63, 67,138,192), in which a copper atom is attached to each C C bond industrial processes to separate dienes from mono-olefins and paraffins are based on this difference in stability (8). Complexes of the type [Cu(un)]+, [CuCl(un)], and [CuCl2(un)] have been shown to exist in dilute acid solution (15, 67, 138). 

Recently, the copper(I) halide-catalyzed arylation procedure has been successfully utilized to incorporate the (Et0)2P(0)CF2 moiety into a variety of biologically active targets. 

Figure 1 Preparation of copper(I)-halide-containing complexes23...

Figure 10 The effect of magic angle spinning on the broad band 63Cu NMR spectrum of powdered copper(I) halide ...

---