α-Halogenoacetanilides as Hydrogen-Bonding Organocatalysts that Activate Carbonyl Bonds: Fluorine versus Chlorine and Bromine

Authors

  • Dr. Sylvain Koeller,

    1. Institut des Sciences Moléculaires, UMR CNRS 5255, Université de Bordeaux, 351 cours de la Libération, 33405 Talence (France), Fax: (+33) 54000-6158
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  • Dr. Coralie Thomas,

    1. Institut des Sciences Moléculaires, UMR CNRS 5255, Université de Bordeaux, 351 cours de la Libération, 33405 Talence (France), Fax: (+33) 54000-6158
    2. Laboratoire de Chimie des Polymères Organiques, UMR 5629, Université de Bordeaux and CNRS, 16 avenue Pey-Berland, 33600 Pessac (France)
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  • Dr. Fréderic Peruch,

    1. Laboratoire de Chimie des Polymères Organiques, UMR 5629, Université de Bordeaux and CNRS, 16 avenue Pey-Berland, 33600 Pessac (France)
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  • Dr. Alain Deffieux,

    1. Laboratoire de Chimie des Polymères Organiques, UMR 5629, Université de Bordeaux and CNRS, 16 avenue Pey-Berland, 33600 Pessac (France)
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  • Dr. Stéphane Massip,

    1. FRE CNRS 3396 Pharmacochimie, Université de Bordeaux, 146 rue Léo Saignat, 33076 Bordeaux (France)
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  • Prof. Dr. Jean-Michel Léger,

    1. FRE CNRS 3396 Pharmacochimie, Université de Bordeaux, 146 rue Léo Saignat, 33076 Bordeaux (France)
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  • Dr. Jean-Pierre Desvergne,

    1. Institut des Sciences Moléculaires, UMR CNRS 5255, Université de Bordeaux, 351 cours de la Libération, 33405 Talence (France), Fax: (+33) 54000-6158
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  • Prof. Dr. Anne Milet,

    1. Département de Chimie Moléculaire, UMR 5250, ICMG FR-2607, Université Joseph Fourier-Grenoble I, BP 53, 38041 Grenoble (France)
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  • Dr. Brigitte Bibal

    Corresponding author
    1. Institut des Sciences Moléculaires, UMR CNRS 5255, Université de Bordeaux, 351 cours de la Libération, 33405 Talence (France), Fax: (+33) 54000-6158
    • Institut des Sciences Moléculaires, UMR CNRS 5255, Université de Bordeaux, 351 cours de la Libération, 33405 Talence (France), Fax: (+33) 54000-6158

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Abstract

α-Halogenoacetanilides (X=F, Cl, Br) were examined as H-bonding organocatalysts designed for the double activation of C[DOUBLE BOND]O bonds through NH and CH donor groups. Depending on the halide substituents, the double H-bond involved a nonconventional C[BOND]H⋅⋅⋅O interaction with either a H[BOND]CXn (n=1–2, X=Cl, Br) or a H[BOND]CAr bond (X=F), as shown in the solid-state crystal structures and by molecular modeling. In addition, the catalytic properties of α-halogenoacetanilides were evaluated in the ring-opening polymerization of lactide, in the presence of a tertiary amine as cocatalyst. The α-dichloro- and α-dibromoacetanilides containing electron-deficient aromatic groups afforded the most attractive double H-bonding properties towards C[DOUBLE BOND]O bonds, with a N[BOND]H⋅⋅⋅O⋅⋅⋅H[BOND]CX2 interaction.

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