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Updated: Oct 7, 2026

Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Experimental evidence supporting a CuIII intermediate in cross-coupling reactions of allylic esters with
1Department of Organic Chemistry, Stockholm University, Sweden.
Abstract:
The reaction between an allylic ester and a magnesium diallylcuprate, or an allylic Grignard reagent in combination with a catalytic amount of a copper salt, has been studied. These reactions yield a mixture of homo- and cross-coupled 1,5-diene products. The product ratios obtained are close to those expected for a reaction proceeding via a triallylcopper(III) intermediate consisting of three equivalent allyl groups bound to copper. When the reaction is performed with a stoichiometric amount of a preformed diallylcuprate, a homo-coupling/cross-coupling ratio larger than that predicted for a CuIII intermediate is observed. However, on dilution this ratio decreases and becomes close to the predicted ratio. The deviation from the predicted homo-coupling/cross-coupling ratio was accounted for by an olefin-induced homo-coupling, as demonstrated in control experiments. The possibility of the allylic ligands to coordinate to the metal center in a eta3 or eta1 fashion provides an opportunity for the stabilization of the intermediate CuIII species.
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