Gilman reagent

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A Gilman reagent is a lithium and copper (diorganocopper) reagent compound, R₂CuLi, where R is an organic radical. These are useful because they react with chlorides, bromides, and iodides to replace the halide group with an R group. This is extremely useful in creating larger molecules from smaller ones.

These reagents were discovered by Henry Gilman. Lithium dimethylcopper (CH₃)₂CuLi can be prepared by adding copper(I) iodide to methyl lithium in tetrahydrofuran at −78 °C. In the reaction depicted below,^[1] the Gilman reagent is a methylating reagent reacting with an alkyne in a conjugate addition, and the negative charge is trapped in a nucleophilic acyl substitution with the ester group forming a cyclic enone.

[edit] See also

• Organolithium reagent
• Organocopper
• Grignard reagent

[edit] External links

• National Pollutant Inventory - Copper and compounds fact sheet

[edit] References

1. ^ Modern Organocopper Chemistry, N. Krause Ed. Wiley-VCH, 2002.

• Henry Gilman, Reuben G. Jones, and L. A. Woods (1952). "The Preparation of Methylcopper and some Observations on the Decomposition of Organocopper Compounds". Journal of Organic Chemistry 17 (12): 1630 - 1634. doi:10.1021/jo50012a009. 
• J. F. Normant (1972). "Organocopper(I) Compounds and Organocuprates in Synthesis". Synthesis 1972: 63-80. doi:10.1055/s-1972-21833. 

v • d • e Concepts in organometallic chemistry Principles Electron counting, 18-Electron rule, Polyhedral skeletal electron pair theory, Isolobal principle, π backbonding, Hapticity Reactions Oxidative addition, Reductive elimination, Beta-hydride elimination, Transmetalation, Carbometalation Types of compounds Gilman reagent, Grignard reagents, Cyclopentadienyl complexes, Metallocenes, Sandwich compound, Transition metal carbene complexes Applications Monsanto process, Ziegler-Natta catalyst, Olefin metathesis Related branches of chemistry Organic chemistry - Inorganic chemistry - Bioinorganic chemistry