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Updated: May 17, 2026

Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Mixed (P=S/P=O)-stabilized geminal dianion: facile diastereoselective intramolecular C-H activations by a related
Hadrien Heuclin1, Xavier F Le Goff, Nicolas Mézailles
1Laboratoire Hétéroéléments et Coordination, Ecole Polytechnique, CNRS, Route de Saclay, 91120 Palaiseau, France.
Abstract:
A new unsymmetrical geminal dianion that contained both a phosphine oxide moiety and a phosphine sulfide moiety has been synthesized. Its reactivity towards Ru(II) was explored, which led to the formation of a highly reactive carbene complex that evolved at room temperature to yield a kinetic orthometalated Ru(II) complex through C-H activation of the phenyl group of the phosphine oxide moiety. This insertion was found to be thermally reversible and a second C-H insertion occurred at a phenyl group of the phosphine sulfide moiety to form the thermodynamic orthometalated Ru(II) complex in a diastereospecific manner. DFT calculations fully rationalized the experimental findings in terms of the relative energies of the kinetic and thermodynamic products and allowed the mechanism of this process to be fully understood.
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