Gilman reagents conjugate additions

Coniine, molecular model of. 28 structure of, 294 Conjugate acid, 49 Conjugate base, 49 Conjugate carbonyl addition reaction, 725-729 amines and, 727 enamines and, 897-898 Gilman reagents and, 728-729 mechanism of, 725-726 Michael reactions and, 894-895 water and. 727 Conjugated diene, 482... 

The related 6-trifluoromethyl-l,3-dioxin-4-ones underwent conjugate addition reactions with Gilman reagents, or with Grignards with copper(I) catalysis (Eq. 112). The 6-substituted compounds were also available, and were used to synthesise threonine and aZZo-threonine analogues [303]. Stark contrast between the behaviour of fluorinated and non-fluorinated compounds is revealed in Eq. (113). While benzylmagnesium chloride adds smoothly to the 6-methyl... 

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... 

Scheme 10. Working hypothesis for the o-DPPB group to act as an organometallic reagent directing group for the conjugate addition of Gilman cuprates to acyclic enoates.

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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