How to prepare gilman reagent from grignard reagent?
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A Gilman reagent is a lithium and copper(diorganocopper) reagent compound, R2CuLi, where R is an alkyl or aryl. These reagents are useful because, unlike related Grignard reagents and organolithium reagents, they react with organic halides to replace the halide group with an R group (the Corey-House reaction). Such displacement reactions allow for the synthesis of complex products from simple building blocks.Generalized chemical reactionshowing Gilman reagent reacting with organic halide to form products and showing Cu(III) reaction intermediate.
These reagents were discovered by Henry Gilman and coworkers. Lithium dimethylcopper (CH3)2CuLi can be prepared by adding copper(I) iodide to methyllithium in tetrahydrofuran at −78 °C. In the reaction depicted below, 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 substitutionwith the ester group forming a cyclic enone.
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A Gilman reagent is a lithium and copper(diorganocopper) reagent compound, R2CuLi, where R is an alkyl or aryl. These reagents are useful because, unlike related Grignard reagents and organolithium reagents, they react with organic halides to replace the halide group with an R group (the Corey-House reaction). Such displacement reactions allow for the synthesis of complex products from simple building blocks.Generalized chemical reactionshowing Gilman reagent reacting with organic halide to form products and showing Cu(III) reaction intermediate.
These reagents were discovered by Henry Gilman and coworkers. Lithium dimethylcopper (CH3)2CuLi can be prepared by adding copper(I) iodide to methyllithium in tetrahydrofuran at −78 °C. In the reaction depicted below, 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 substitutionwith the ester group forming a cyclic enone.
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Preparation of Gilman Reagent
Gilman reagent can be prepared in two steps: First, by adding powdered lithium metal to alkyl halide in pentane solvent. Second, by adding copper(I) bromide to alkyllithium in tetrahydrofuran at −78 °C.
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