Organolithium reagents, reaction with vinyl ethers

Like magnesium, lithium reacts with alkyl halides, vinyl halides, and aryl halides to form organometallic compounds. Ether is not necessary for this reaction. Organolithium reagents are made and used in a wide variety of solvents, including alkanes. 

The cyclic vinyl ether 2,3-dihydro-1,4-dioxin is converted into its cyclic hemiacetal hydration product, tetrahydro-2-hydroxy-1,4-dioxin, in aqueous solution by an acid-catalyzed reaction <870K2746, 89JP043). Treatment of an alcohol with excess of 2,3-dihydro-1,4-dioxin at room temperature in the presence of copper(II) bromide in tetrahydrofuran leads to the corresponding acetal. This new protective group for alcohols, which is stable towards lithium aluminum hydride and organolithium reagents, can be removed by treatment with acidified aqueous methanol <85S806>. 

Organolithium compounds and Grignard reagents are prepared by reaction of the metal with an alkyl, aryl, or vinylic halide, usually in diethyl ether or tetrahydrofuran as the solvent. 

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