Organolithium compounds coupling with halides

Organolithium compounds, acetylenic, reaction with ketones, 163 carbonation, 424 coupling with halides, 9, 10, 11 olefinic, reaction with aldehydes, 160... 

A variety of organometallic compoundshave been used to couple with alkyl halides. " Organosodium and organopotassium compounds are more reactive than Grignard reagents and couple even with less reactive halides. Organolithium... 

Murahashi, S.-l. Palladium-catalyzed cross-coupling reaction of organic halides with Grignard reagents, organolithium compounds and heteroatom nucleophiles. J. Organomet. Chem. 2002, 653, 27-33. 

Gilman reagents giving the best yields of coupling products are those prepared from methyl, primary alkyl, allylic, vinylic, and aryl halides via the corresponding organolithium compounds. Yields are lower with secondary and tertiary haloalkanes. 

The organolithium compounds formed by the reaction shown in eq. (3.1 ) tend to react with hydrocarbon halides by the Wurts coupling reaction and the yields of organolithium compounds are low if the resultant organolithium compounds are very reactive compounds such as allylithium or benzyllithium. Hence, for these reactions, transmetalation reactions, as described below are used. Therefore, this reaction is used for production of organolithium compounds having relatively low reactivity such as alkyllithiums, vinyllithiums and aryllithiums [14—20]. 

The acidic OH makes it impossible to prepare an organolithium reagent from this aryl halide, so this compound must be used as the aryl halide that couples with the organoborane from bromobenzene. 

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