Reactions of Gilman Reagents

A Gilman reagent couples with alkyl halides, alkenyl halides (vinyl halides), and aryl halides. 

The Gilman reagent has been used in the industrial synthesis of muscalure, the sex attractant of the common house-fly. Muscalure is added to fly bait that also contains an insecticide. When the fly eats the bait, the attraction is fatal. 

The Gilman reagents also undergo coupling reactions with aryl halides. For example, bromobertzene reacts with lithium dimethylcuprate to give toluene. 

When we discuss a,P-unsaturated carbonyl compounds in Chapter 21, we will find that Gilman reagents selectively add to the P-carbon, in conttast to Grignard reagents, which add to the carbonyl group. Here is a preview  

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Under the conditions of a rapid injection experiment, the conjugate addition reactions of Gilman reagents (177) (X = CN or I) with cyclohex-2-enone has been studied in detail. Formation of various species (178-181) and the oscillation of their concentrations have been monitored by XH NMR spectroscopy (Scheme 9).212... 

The reaction of Gilman reagents with ,)8 -epoxy-oximes yields -hydroxy-ketones [e.g. (17 X=OH)].56 Vinyl copper compounds are converted stereo-specifically into /3,/3-disubstituted a-ethylenic acids by carbonation nerol (18) was synthesized (Scheme 3).57 Further papers on /3-ketosulphoxide synthesis [e.g. of... 

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