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Updated: Jun 6, 2026

Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Double Friedel-Crafts acylation reactions on the same ring of a metallocene: synthesis of a
Duncan Carmichael1, Pascal Le Floch, Xavier F Le Goff
1Laboratoire Hétéroéléments et Coordination, Ecole Polytechnique, CNRS, 91128 Palaiseau cedex, France. duncan.carmichael@polytechnique.edu
Abstract:
The synthetic outcome of the Friedel-Crafts acylation of 1',2',3,3',4,4',5'-heptamethylphospharuthenocene reflects the nature of the acylating agent, with alkanoyl anhydride/trifluoromethanesulfonic acid (TfOH) reagents giving monosubstitution at the phospholyl ring, whereas alkanoyl chloride/AlCl(3) gives 2,5-disubstitution. DFT calculations indicate that this unusual double acylation can be facilitated by the intervention of the phosphorus atom at an early stage in the reaction trajectory, with the acyl group being delivered from the phosphorus atom into the ring 2- or 2,5-positions.
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