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Double Friedel–Crafts Acylation Reactions on the Same Ring of a Metallocene: Synthesis of a 2,5-Diacetylphospharuthenocene

Authors

  • Dr. Duncan Carmichael,

    Corresponding author
    1. Laboratoire “Hétéroéléments et Coordination”, Ecole Polytechnique, CNRS, 91128 Palaiseau cedex (France), Fax: (+33) 169334440
    • Laboratoire “Hétéroéléments et Coordination”, Ecole Polytechnique, CNRS, 91128 Palaiseau cedex (France), Fax: (+33) 169334440
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  • Prof. Dr. Pascal Le Floch,

    1. Laboratoire “Hétéroéléments et Coordination”, Ecole Polytechnique, CNRS, 91128 Palaiseau cedex (France), Fax: (+33) 169334440
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    • Pascal le Floch died on March 17, 2010.

  • Dr. Xavier F. Le Goff,

    1. Laboratoire “Hétéroéléments et Coordination”, Ecole Polytechnique, CNRS, 91128 Palaiseau cedex (France), Fax: (+33) 169334440
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  • Dr. Olivier Piechaczyk,

    Corresponding author
    1. Laboratoire “Hétéroéléments et Coordination”, Ecole Polytechnique, CNRS, 91128 Palaiseau cedex (France), Fax: (+33) 169334440
    • Laboratoire “Hétéroéléments et Coordination”, Ecole Polytechnique, CNRS, 91128 Palaiseau cedex (France), Fax: (+33) 169334440
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  • Dr. Nicolas Seeboth

    1. Laboratoire “Hétéroéléments et Coordination”, Ecole Polytechnique, CNRS, 91128 Palaiseau cedex (France), Fax: (+33) 169334440
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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/AlCl3 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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