Gilman reagent

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General structure of a Gilman reagent

A Gilman reagent is a

aryl. They are colorless solids[citation needed
].

Use in organic chemistry

A conjugated 1,4 addition using a Gilman reagent with an arbitrary R group

These reagents are useful because, unlike related

halide group with an R group (the Corey–House reaction). Such displacement reactions allow for the synthesis of complex products from simple building blocks.[1][2] Lewis acids can be used to modify the reagent.[2]


Generalized
organic halide to form products and showing Cu(III) reaction intermediate

History

These reagents were discovered by

enone
.

Scheme 1. Example Gilman reagent reaction
Scheme 1. Example Gilman reagent reaction

Structure

Lithium dimethylcuprate exists as a

dimer in diethyl ether forming an 8-membered ring. Similarly, lithium diphenylcuprate crystallizes as a dimeric etherate, [{Li(OEt2)}(CuPh2)]2.[5]

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

If the Li+ ions is complexed with the

12-crown-4, the resulting diorganylcuprate anions adopt a linear coordination geometry at copper.[6]

Dimethylcuprate anion from crystal structure Diphenylcuprate anion from crystal structure

For the higher order cyanocuprate Li2CuCN(CH3)2, the cyanide ligand is coordinated to Li and π-bound to Cu.[7]

Mixed cuprates

More useful generally than the Gilman reagents are the so-called mixed cuprates with the formula [RCuX]− and [R2CuX]2−. Such compounds are often prepared by the addition of the organolithium reagent to copper(I) halides and cyanide. These mixed cuprates are more stable and more readily purified.[8] One problem addressed by mixed cuprates is the economical use of the alkyl group. Thus, in some applications, the mixed cuprate has the formula Li
2[Cu(2-thienyl)(CN)R] is prepared by combining thienyllithium and cuprous cyanide followed by the organic group to be transferred. In this higher order mixed cuprate, both the cyanide and thienyl groups do not transfer, only the R group does.[9]

See also

External links

References

  1. doi:10.1055/s-1972-21833
    .
  2. ^
    ISSN 1460-4744
    .
  3. doi:10.1021/jo50012a009.{{cite journal}}: CS1 maint: multiple names: authors list (link
    )
  4. ^ Modern Organocopper Chemistry, N. Krause Ed. Wiley-VCH, 2002.
  5. doi:10.1002/anie.199003001
    .
  6. doi:10.1021/ja00300a047
    .
  7. doi:10.1021/jo00104a009.{{cite journal}}: CS1 maint: multiple names: authors list (link
    )
  8. doi:10.1002/047084289X.rc224.pub2
  9. doi:10.15227/orgsyn.069.0080
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