Gilman reagent reaction with enones

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... 

A less general method involves transfer of a chiral group from the cuprate to the enone. The chiral Gilman reagent [R 2CuLi, R = (R)-2-(l-dimethylamino)phenyl] reacted with (4 )-methyl-3-penten-2-one (473) to give 474 in 30% yield and 80% ee. 33 Reaction of the mixed cuprate [ThR CuLi where Th = 2-thienyl and R = (R)-2-(l-dimethylamino)phenyl] gave 474 in 70% yield (82% ee). 3... 

The copper-catalyzed 1,4-addition of Grignard reagents to enones has been described by Kharasch in 1941, that is, one decade before the discovery of Gilman cuprates (1952) and more than two decades before the first use of organocuprates in conjugate addition reactions. Consequently, numerous variations and applications of the method have been reported over the years.3 5,7 7a 23 Not surprisingly, several of the advances made in the last decade with... 

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