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 methyllithium in tetrahydrofuran at -78°C. In the reaction depicted in scheme 1 ^[1] the Gilman reagent is a methylating reagent reacting with an alkyne in an 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
• Grignard reagent

[edit] External links

• National Pollutant Inventory - Copper and compounds fact sheet

• Links to external chemical sources.

[edit] References

1. ↑  Conjugate addition-cycloacylation of acetylenic diesters: synthesis of highly functionalized cyclopentenones Michael T. Crimmins, S. Wayne Mascarella, Joe A. DeLoach J. Org. Chem.; 1984; 49(16); 3033-3035. Abstract
2. ↑  Modern Organocopper Chemistry, N. Krause Ed. Wiley-VCH, 2002.