Sec-Butyllithium

sec-Butyllithium is an organometallic compound with the formula CH₃CHLiCH₂CH₃, abbreviated sec-BuLi or s-BuLi. This chiral organolithium reagent is used as a source of sec-butyl carbanion in organic synthesis.

Synthesis

sec-BuLi can be prepared by the reaction of sec-butyl halides with lithium metal:

Properties

Physical properties

sec-Butyllithium is a colorless viscous liquid. Using mass spectrometry, it was determined that the pure compound has a tetrameric structure. It also exists as tetramers when dissolved in organic solvents such as benzene, cyclohexane or cyclopentane. The cyclopentane solution has been detected with ⁶Li-NMR spectroscopy to have a hexameric structure at temperatures below −41 °C. In electron-donating solvents such as tetrahydrofuran, there exists an equilibrium between monomeric and dimeric forms.

Chemical properties

The carbon-lithium bond is highly polar, rendering the carbon basic, as in other organolithium reagents. Sec-butyllithium is more basic than the primary organolithium reagent, n-butyllithium. It is also more sterically hindered. sec-BuLi is employed for deprotonations of particularly weak carbon acids where the more conventional reagent n-BuLi is unsatisfactory. It is, however, so basic that its use requires greater care than for n-BuLi. For example diethyl ether is attacked by sec-BuLi at room temperature in minutes, whereas ether solutions of n-BuLi are stable.

The compound decomposes slowly at room temperature and more rapidly at higher temperatures, giving lithium hydride and a mixture of butenes.

Applications

Many transformations involving sec-butyllithium are similar to those involving other organolithium reagents.

In combination with sparteine as a chiral auxiliary, sec-butyllithium is useful in enantioselective deprototonations. It is also effective for lithiation of arenes.

References