Master Organic Chemistry Reaction Guide

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)

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(Advanced) References and Further Reading

  1. 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
    DOI: 10.1021/jo50012a009
    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:
  2. 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
    DOI: 10.1021/ja00458a015
  3. 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
  4. 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
    DOI: 10.1021/jo01348a012
  5. 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
  6. 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
    DOI: 10.1021/jo01267a004




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