Formation of Gilman reagents (organocuprates) from alkyl halides
Description: Alkyl halides will react with lithium metal (Li) to make organolithium reagents. When two equivalents of organolithium are combined with a copper halide, this will form organocuprates (Gilman reagents)
Content available for Reactionguide members only. Not a member? Get access for about 30 cents / day!
(Advanced) References and Further Reading
- The Preparation of Methylcopper and some Observations on the Decomposition of Organocopper Compounds
Henry Gilman, Reuben G. Jones, and L. A. Woods.
The Journal of Organic Chemistry 1952 17 (12), 1630-1634
One of the first papers by Prof. Henry Gilman (U. of Iowa) on ‘Gilman Reagents’ – diorganocopper compounds. In this case he describes the preparation of dimethylcopper.Over the decades, a lotof people have carried out a lot of work in order to elucidate the true nature of copper intermediates and various copper species in reactions. There is a lot of literature in this area, and this is barely scratching the surface:
- The composition of lithium methylcuprates in ether solvents
C. Ashby and John J. Watkins.
Journal of the American Chemical Society 1977 99 (16), 5312-5317
- Mechanism of thermal decomposition of n-butyl(tri-n-butylphosphine) copper(I)
George M. Whitesides, Erwin R. Stedronsky, Charles P. Casey, and Joseph San Filippo Jr.
Journal of the American Chemical Society 1970 92 (5), 1426-1427
- The Chemistry of Carbanions. XII. The Role of Copper in the Conjugate Addition of Organometallic Reagents1
Herbert O. House, William L. Respess, and George M. Whitesides.
The Journal of Organic Chemistry 1966 31 (10), 3128-3141
- Autocatalytic decomposition of alkylcopper(I) species. Electron spin resonance spectrum of binuclear copper(O) intermediates
Jay K. Kochi, Keisuke Wada, and Masuhiko Tamura.
Journal of the American Chemical Society 1970 92 (22), 6656-6658
- Chemistry of carbanions. XVII. Addition of methyl organometallic reagents to cyclohexenone derivatives
Herbert O. House and William F. Fischer Jr.
The Journal of Organic Chemistry 1968 33 (3), 949-956