Gilman reagent

Gilman reagent

Organometallic Compounds

Published in Michael B. Smith, A Q&A Approach to Organic Chemistry, 2020

To honor the work of Henry Gilman, the organocuprate reagent R2CuLi is commonly referred to as a Gilman reagent. How are organocuprates named?

The interaction of carbon-centered radicals with copper(I) and copper(II) complexes*

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Journal Information

Published in Journal of Coordination Chemistry, 2018

Thomas G. Ribelli, Krzysztof Matyjaszewski, Rinaldo Poli

A series of elusive [CuIIIR4]– [63], [CuIIIR3(X)]– (X = halide, CN, SCN, SPh, PPh2, etc.) [63–66], [LCuIIIR3] [67] and [(η3-allyl)CuIIIR2] [68] complexes with non-fluorinated alkyl groups were generated in the Bertz group from Gilman’s reagent (Me2CuLi) or from the cyano Gilman reagent (Me2CuLi·LiCN) by rapid injection techniques at low temperature (–100 °C) and characterized by nuclear magnetic resonance (NMR) spectroscopy. One example (3) is detailed in Figure 2 [64, 69]. The stability of these systems depends on the nature of the ancillary ligands, but decomposition generally occurs upon warming above –80 °C to generate products of alkyl-alkyl reductive elimination. Complex [CuIIIMe4]–, prepared in high yields from [Me2CuLi·LiX] and MeLi in a 1:2 ratio at –100 °C, was surprisingly stable (t1/2 = 7 h at 0 °C, 0.75 h at 20 °C) [70]. Note that these stabilized organocopper(III) species containing two or more alkyl groups spontaneously degrade by alkyl-alkyl reductive elimination, Equation (14), and that this chemistry does not involve radicals (see also Section B.5).

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Organometallic Compounds

The interaction of carbon-centered radicals with copper(I) and copper(II) complexes*