Copper iodide, complexes from

A similar mixed ox a- thia macrocycle incorporating a rigid horseshoeshaped aromatic moiety, l,ll,21-trioxa-8,14-dithia[2,9,2]paracyclophane, L40, has been synthesized and reacted with copper iodide in MeCN solution (Scheme 19).160 Its polymeric copper iodide complex [Cu4I4(L40)2] 40 crystallizes, in a 2 1 metal to ligand ratio, as an ID infinite array of cubane-like units consisting of four copper atoms, four i3-iodine atoms, and four sulfur atoms, stemming from four different macrocycles. The Cu—Cu distances are about 2.731 A. Unfortunately, the photophysics of this compound have not been studied. 

This complex should be used when the organolithium is in solution in a hydrocarbon solvent. For organolithium reagents prepared in ether (see Note 4), the same complex may be used or, more conveniently, copper iodide (Cull can be used. The Cul purchased from Prolabo or Merck 4 Company, Inc. may be used directly. Other commercial sources of Cul (Fluka, Aldrich Chemical Company, Inc., Alfa Products, Morton/Thiokol, Inc.) furnish a salt which affords better results when purified. 1 mol of Cul is stirred for 12 hr with 500 ml of anhydrous tetrahydrofuran, then filtered on a sintered glass funnel ( 3), washed twice with 50 ml of anhydrous tetrahydrofuran, once with 50 ml of anhydrous ether and finally dried under reduced pressure (0.1 imO for 4 hr. 

Copper-mediated coupling of the aryl iodide derived from l,3-bis(2-hydroxy-hexafluoroisopropyl)benzene with perfluorooctyl iodide gives the desired compound as a dimethyl sulfoxide (DMSO) complex [166] (equation 143) Even bromoarenes can be coupled [167] (equation 144)... 

More useful for synthetic purposes, however, is the combination of the zinc-copper couple with methylene iodide to generate carbene-zinc iodide complex, which undergoes addition to double bonds exclusively to form cyclopropanes (7). The base-catalyzed generation of halocarbenes from haloforms (2) also provides a general route to 1,1-dihalocyclopropanes via carbene addition, as does the nonbasic generation of dihalocarbenes from phenyl(trihalomethyl)mercury compounds. Details of these reactions are given below. 

CH3(CH2)4CH = CHCH = CHC00CH2CH3, C12H20O2, Mr 196.29, bp6i> 70-72 °C, has been identified in pears and has the typical aroma of Williams pears. Synthesis of ethyl 2-trans-4-cw-decadienoate starts from cis-l-heptenyl bromide, which is converted into a 1-heptenyllithium cuprate complex with lithium and copper iodide. Reaction with ethyl propiolate yields a mixture of 95% ethyl 2-trans-A-cis- and 5% ethyl 2-tranx-4-tranx-decadienoate. Pure ethyl 2-trans-A-cis-decadienoate is obtained by fractional distillation [25]. A biotechnological process for its preparation has been developed [26]. 

Tanaka reported the synthesis of (/ )-muscone (10) by an enantioselective conjugate addition of chiral alkoxydimethylcuprate, which was prepared from chiral ercdo-3-[(l-methylpyrrol-2-yl)methylamino]-l,7,7-trimethylbicyclo[2.2.1]heptan-2-ol (9), methyllithium, and copper iodide (Scheme 9.7) [16]. In this reaction, convex deviation from a linear correlation was observed when the chiral ligand had a higher enantiopurity. This positive NLE was probably induced by the formation of a reactive homochiral dinuclear copper complex to give (R)-muscone. Rossitter also observed asymmetric amplification in a copper-catalyzed conjugate addition of methyl-... 

There is continued expansion in the use of metals as catalysts in substitution reactions. Copper iodide in the presence of /V./V -dimcthylcthylcncdiamine has been shown to be effective in the intramolecular substitution of aryl bromides carrying an o-l,3-dicarbonyl substituent reaction may involve either an oxygen centre or a carbon centre of the dicarbonyl moiety.26 The reaction of aryl halides with sodium trifluoroacetate in the presence of copper iodide may lead to the formation of the tri-fluoromethylated derivatives, possibly via CF3CuI as an intermediate.27 There have been theoretical calculations, PM3 and ab initio, on complexes formed from copper... 

The nature of organocopper reagents appears to be dependent on the method of preparation and the stoichiometry. Specific examples are methylcopper (76, 310), phenylcopper 73), and pentafluorophenyl-copper 34, 37, 147). The best method of preparing pentafluorophenyl-copper of composition CeFsCu appears to be via the addition of copper(I) bromide to pentafluorophenylmagnesium bromide 34, 37), since the lithium reagent and copper iodide gives an ate complex 147). An ate complex was also obtained from pentafluorophenyllithium and silver chloride in equimolar proportions 265). As shown in Table III, many of the isolated copper compounds gave somewhat incorrect or irreproducible analyses, and others contain metal halide and solvent molecules. 

The reaction of molten Htmpz with copper metal shot in air yielded a mixture of the trinuclear copper(I) complex [Cu(tmpz)]3, 11, and the trinuclear cop-per(l/Il) complex [Cu(3-C02-4,5-Me2pz)(Htmpz)]2Cu in which the 3-C02-4,5-Me,pz ligand, derived from the oxidation of one of the three methyl groups of the tmpz, is present (25). Alternatively, 11 was prepared by reacting cuprous iodide with Htmpz in the presence of triethylamine (26). The structure of 11 is... 

Antimony can be separated from bismuth by extraction into benzene from iodide medium. From 5 M H2SO4 and 0.05 M KI solution, Sbli is extracted in a good yield, whereas the bismuth complex is not extracted at all. Thallium is precipitated as T1(I) and separated by filtration [36]. Copper is masked with thiourea. 

Copper is removed by masking the mercury as strong bromide- or iodide complexes in acid media. Only copper dithizonate is extracted from 1 M HCl containing KI. Alternatively, the mercury and copper can be extracted from acid solution, and the mercury stripped with an acidic solution of KI or KBr. The mercury is re-extracted from the aqueous... 

Acylation of copper derivatives with acid chlorides works well, but they do not react with free carboxylic acids, unlike the more basic alkyl-lithiums. A dramatic illustration of chemoselectivity comes in the interaction of Bu2CuLi with the free acid 59 and its acid chloride 61. Reaction occurs24 at the alkyl iodide with the one to give 60 and at the acid chloride with the other to give the ketone 62. Acylation can also be achieved by many other metal complexes, from A1 to Zr, but to make those we need hydrometallation, the subject of the next section. 

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