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Gilman reagent

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Title: Gilman reagent  
Author: World Heritage Encyclopedia
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Subject: Wender Taxol total synthesis, Organocopper compound, Lithium compounds, Lithium, Henry Gilman
Collection: Lithium Compounds, Organocopper Compounds, Reagents for Organic Chemistry
Publisher: World Heritage Encyclopedia

Gilman reagent

General structure of a Gilman reagent

A Gilman reagent is a chlorides, bromides, and iodides to replace the halide group with an R group. This is extremely useful in creating larger molecules from smaller ones.[1]

Generalized reaction intermediate

These reagents were discovered by Henry Gilman.[2] Lithium dimethylcopper (CH3)2CuLi can be prepared by adding copper(I) iodide to methyllithium in tetrahydrofuran at −78 °C. In the reaction depicted below,[3] 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.

Scheme 1. Example Gilman reagent reaction

Gilman reagents have complicated structures in crystalline form and in solution. Lithium dimethylcuprate is a dimer in diethyl ether forming an 8-membered ring with two lithium atoms coordinating between two methyl groups. Similarly, lithium diphenylcuprate forms a dimeric etherate, [{Li(OEt2)}(CuPh2)]2, in the solid state.[4]

Lithium diphenylcuprate etherate dimer from crystal structure - 3D stick model Skeletal formula of lithium diphenylcuprate etherate dimer

If the Li+ ions are rendered inert by complexation with the coordination geometry at copper.[5]

Dimethylcuprate anion from crystal structure Diphenylcuprate anion from crystal structure

See also

External links

  • National Pollutant Inventory - Copper and compounds fact sheet


  1. ^ J. F. Normant (1972). "Organocopper(I) Compounds and Organocuprates in Synthesis". Synthesis 1972 (02): 63–80.  
  2. ^  
  3. ^ Modern Organocopper Chemistry, N. Krause Ed. Wiley-VCH, 2002.
  4. ^ N. P. Lorenzen, E. Weiss (1990). "Synthesis and Structure of a Dimeric Lithium Diphenylcuprate:[{Li(OEt)2}(CuPh2)]2".  
  5. ^ H. Hope, M. M. Olmstead, P. P. Power, J. Sandell, X. Xu (1985). "Isolation and x-ray crystal structures of the mononuclear cuprates [CuMe2], [CuPh2], and [Cu(Br)CH(SiMe3)2]".  
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