Vinyllithium is an organolithium compound with the formula LiC2H3. A colorless or white solid, it is encountered mainly as a solution in tetrahydrofuran (THF). It is a reagent in synthesis of organic compounds, especially for vinylations.
Preparation and structure
Solutions of vinyllithium are prepared by lithium-halogen exchange reactions. A halide-free route entails reaction of tetravinyltin with butyllithium:
Sn(CH=CH2)4 + 4 BuLi → SnBu4 + 4 LiCH=CH2The reaction of ethylene and lithium affords vinyl lithium and lithium hydride, together with other organolithium compounds,2
Like most organolithium compounds, vinyllithium crystallizes from THF as a cluster compound as a cubane-type cluster.3
Reactions
Vinyllithium is used to install vinyl groups on metal-based reagents, i.e., vinylations. It is a precursor to vinylsilanes, vinylcuprates, and vinylstannanes.4 It adds to ketones compounds to give allylic alcohols. Vinylmagnesium bromide is often used in place of vinyllithium.5
Alternative reagents
Vinyl magnesium bromide, a Grignard reagent, is in many ways easier to generate in the laboratory and behaves similarly to vinyllithium.6
References
Eisenhart, Eric K.; Bessieres, Bernard (2007). "Vinyllithium". E-EROS Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rv015.pub2. ISBN 978-0-471-93623-7.. 978-0-471-93623-7 ↩
Eisenhart, Eric K.; Bessieres, Bernard (2007). "Vinyllithium". E-EROS Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rv015.pub2. ISBN 978-0-471-93623-7.. 978-0-471-93623-7 ↩
Walter Bauer; Frank Hampel (1992). "X-Ray crystal structure of a vinyllithium–tetrahydrofuran solvate (C2H3Li–thf)4. Quantitative estimation of Li–H distances by 6Li–1H HOESY". J. Chem. Soc., Chem. Commun. (12): 903–905. doi:10.1039/C39920000903. /wiki/Doi_(identifier) ↩
Lipshutz, Bruce H.; Moretti, Robert; Crow, Robert (1990). "Mixed Higher-order Cyanocuprate-induced Epoxide Openings: 1-benzyloxy-4-penten-2-ol". Org. Synth. 69: 80. doi:10.15227/orgsyn.069.0080. /wiki/Doi_(identifier) ↩
Dietmar Seyferth (1959). "Di-n-butyldivinyltin". Org. Synth. 39: 10. doi:10.15227/orgsyn.039.0010. /wiki/Doi_(identifier) ↩
William J. Scott, G. T. Crisp, J. K. Stille (1990). "Palladium-catalyzed Coupling of Vinyl Triflates with Organostannanes: 4-tert-Butyl-1-Vinylcyclohexene and 1-(4-tert-Butylcyclohexen-1-yl)-2-propen-1-one". Organic Syntheses. 68: 116. doi:10.15227/orgsyn.068.0116.{{cite journal}}: CS1 maint: multiple names: authors list (link) /wiki/Doi_(identifier) ↩