Organolithium reagents-Copper halides

Lithium dialkylcuprates-Boron trifluoride etherate, 208 Lithium diallylcuprate, 11 Lithium dibutylcuprate, 61, 208, 344 Lithium dibutylcuprate-Boron trifluoride etherate, 208 Lithium dimethylcuprate, 63, 151, 258 Lithium dimethylcuprate-Boron trifluoride etherate, 208 Organocopper reagents, 11, 61, 63, 131, 151, 207, 344 Organocopper reagents-Boron trifluoride etherate, 208 Organolithium reagents-Copper(I) halides, 58... 

The stoichiometric reaction of organolithium or Grignard reagents with copper halides allows direct formation of organocopper species(103). 

Lithium butyldimethylzincate, 221 Lithium sec-butyldimethylzincate, 221 Organolithium reagents, 94 Organotitanium reagents, 213 Palladium(II) chloride, 234 Titanium(III) chloride-Diisobutylalu-minum hydride, 303 Tributyltin chloride, 315 Tributyl(trimethylsilyl)tin, 212 3-Trimethylsilyl-l, 2-butadiene, 305 Zinc-copper couple, 348 Intramolecular conjugate additions Alkylaluminum halides, 5 Potassium t-butoxide, 252 Tetrabutylammonium fluoride, 11 Titanium(IV) chloride, 304 Zirconium(IV) propoxide, 352 Miscellaneous reactions 2-(Phenylseleno)acrylonitrile, 244 9-(Phenylseleno)-9-borabicyclo[3.3.1]-nonane, 245 Quina alkaloids, 264 Tributyltin hydride, 316 Conjugate reduction (see Reduction reactions)... 

The reaction of organolithiums or organomagnesium halide reagents with gold halides proceeds similarly to the copper halides in a 1 1 ratio. Their phosphine complexes can be isolated and characterized. In a 2 1 ratio, the transmetallation reaction is followed by ate complexation to form organoaurate complexes ... 

Specifically, if two equivalents of n-butyllithium (28) react with Cul, the product is lithium dibutylcuprate (47). Note the nomenclature that is used, where the alkyl unit of the organolithium reagent is combined with term cuprate, which describes the oxidation state of the copper. The carbon attached to copper in 47 is 6- (it is carbanionic), and organocuprates such as 47 are very reactive with most alkyl halides, leading to the coupling product. In one experiment, 47 was formed in THF at -78°C and then treated with 1-iodoheptane as the temperature was allowed to rise to 0°C. The product of this reaction is undecane (48), isolated in 53% yield. ... 

Lithium dialkylcuprates and diarylcuprates (R2CuLi and Ar2CuLi) are prepared by the reaction of a copper(I) salt with two equivalents of the corresponding organolithium reagent and undergo cross-coupling with primary alkyl halides and aryl and vinylic halides. 

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