BIPNOR: A New, Efficient Bisphosphine Having Two Chiral, Nonracemizable, Bridgehead Phosphorus Centers for Use in Asymmetric Catalysis

Authors

  • Frédéric Robin,

    1. Laboratoire “Hétéroéléments et coordination” URA CNRS 1499, DCPH, Ecole Polytechnique, 91128 Palaiseau cedex (France) Fax: Int. code +(1)6933–3990
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  • Dr. François Mercier,

    1. Laboratoire “Hétéroéléments et coordination” URA CNRS 1499, DCPH, Ecole Polytechnique, 91128 Palaiseau cedex (France) Fax: Int. code +(1)6933–3990
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  • Dr. Louis Ricard,

    1. Laboratoire “Hétéroéléments et coordination” URA CNRS 1499, DCPH, Ecole Polytechnique, 91128 Palaiseau cedex (France) Fax: Int. code +(1)6933–3990
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  • Prof. Dr. François Mathey,

    Corresponding author
    1. Laboratoire “Hétéroéléments et coordination” URA CNRS 1499, DCPH, Ecole Polytechnique, 91128 Palaiseau cedex (France) Fax: Int. code +(1)6933–3990
    • Laboratoire “Hétéroéléments et coordination” URA CNRS 1499, DCPH, Ecole Polytechnique, 91128 Palaiseau cedex (France) Fax: Int. code +(1)6933–3990
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  • Dr. Michel Spagnol

    1. Rhǒne-Poulenc, CRIT, 85 Av. des Frères Perret, BP62 69192 Saint-Fons Cedex (France)
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Abstract

Optically active phosphorus ligands are widely used in homogeneous asymmetric catalysis. However, among the numerous available structures of this type, the subclass of optically active bisphosphines with at least one chiral phosphorus atom is rather underdeveloped. A bisphosphine with two chiral, nonracemizable bridgehead phosphorus centers, (meso,d/l)-2,2′,3,3′-tetraphenyl-4,4′,5,5′-tetramethyl-6,6′-bis-1-phosphanorborna-2,5-dienyl (BIPNOR), can be obtained by thermolysis of 1,1′-bisphospholyl with diphenylacetylene. Here, we report the resolution of the d/l isomer by means of a chiral palladium complex to give the two optically active forms of BIPNOR. We then investigate the catalytic properties of BIPNOR, incorporated in RhI and RuII catalysts for the hydrogenation of olefins and ketones and in a PdII catalyst for asymmetric alkylation reactions. BIPNOR is shown to give good results in these catalytic reactions.

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