Synthesis reaction with organolithium compounds

Stadlwieser J, Barbler P, Taylor S (1998) 8-Fluoro-6-(methoxymethoxy)-quinoline synthesis and regioselective functionalization via reaction with organolithium compounds. Helv Chim Acta 81 1088-1094... 

Although the early literature records a number of examples of the synthesis of ketones by reactions of Grignard reagents with carboxylic acids or metal carboxylates [A], this method has been generally found less satisfactory than the corresponding reaction of organolithium compounds [G, 13]. However, it has been reported that reactions of halomagnesium... 

As described in Section II.A, the tandem sequence reaction of organolithium compounds with carbon monoxide followed by reaction with suitable electrophiles provides an useful tool for the preparation of diphenyldialkyl carbinols, and the reaction could be easily extended to produce substituted cyclic ethers in a one-pot synthesis. Thus, by carrying out the carbonylation of phenyllithium in the presence of conveniently substituted chloroalkyl bromides, Br(CH2)3+ Cl, at -78 °C, the oxo-lithiated intermediates 243 are obtained and cyclized to 244 by warming up the reaction mixture (Scheme 74)21. 

Methyl lithium and butyl lithium are widely used for the synthesis of other organolithium compounds. For example, lithium cyclopentadienides are generally prepared by the reaction of the cyclopentadiene with butyl lithium. In contrast, the amido-alkali metal compounds are becoming increasingly important in the synthesis of organoalkali metal compounds with the heavier alkali metals. For example, l,2,4-tris(trimethylsilyl)-l,3-cyclopentadiene reacts with potassium bis(trimethylsilyl)amide to form potassium l,2,4-tris(trimethylsilyl)cyclopentadienide. ... 

Organoselenium compounds are easily attacked by a nucleophile. Reaction with organolithium reagents allows a convenient synthesis of carbanionic species. C. Paulmier and S. Ponthieux describe this chemistry in Chap. 5. 

Athene synthesis. Alcohols can be alkylated or arylated by treatment with organolithium compounds and 1 (equation 1). The main interest in this synthesis is the reaction of allylic alcohols to form alkenes. The reaction is regioselective and stereoselective (inversion of configuration). 

In the synthesis directed towards lincosamine, Szechner [32] utilized a known reaction [33] of lithium salts of carboxylic acids with organolithium compounds (Scheme 14). 

The terminal methyl group of unsymmetrical ketone dimethylhydrazone is reactive, and is easily metalated with organolithium compounds. Subsequently, the substituted products are produced by reaction with halides as shown in eq. (3.25). These reactions are applied for the synthesis of dihydrojasmone [73]. 

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