(Thio)Amidoindoles and (Thio)Amidobenzimidazoles: An Investigation of Their Hydrogen-Bonding and Organocatalytic Properties in the Ring-Opening Polymerization of Lactide

• Published in: Chemistry : a European journal 2010-04, Vol.16 (14), p.4196-4205
• Main Authors: Koeller, Sylvain, Kadota, Joji, Peruch, Frédéric, Deffieux, Alain, Pinaud, Noël, Pianet, Isabelle, Massip, Stéphane, Léger, Jean-Michel, Desvergne, Jean-Pierre, Bibal, Brigitte
• Format: Article
• Language: English
• Subjects: Catalysis; Catalysts; Chemical Sciences; Chemistry; Conversion; Hydrogen bonding; Hydrogen bonds; lactides; Monomers; organocatalysis; partner catalysts; Polymerization; Polymers; Reagents; ring-opening polymerization
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.200902912

The mechanism of the ring‐opening polymerization (ROP) of lactide catalyzed by two partner hydrogen‐bonding organocatalysts was explored. New amidoindoles 4 a,c, thioamidoindoles 4 b,d, amidobenzimidazoles 5 a,c, and thioamidobenzimidazoles 5 b,c were synthesized and used as activators of the monomer. In the solid state and in solution, compounds 4 and 5 showed a propensity for self‐association, which was evaluated. (Thio)Amides 4 and 5 do catalyze the ROP of lactide in the presence of a cocatalyst, tertiary amine 3 a or 3 b, which activates the growing polymer chain through hydrogen‐bonding. Reactions were conducted in 2–24 h at 20 °C; conversion yields ranged between 22 and 100 %. A detailed study of the intermolecular interactions undertaken between the participating species showed that, as expected, simultaneous weak hydrogen bonds do exist to activate the reagents. Moreover, interactions have been revealed between the partner catalysts 4/5+3. ROP catalyzed by these partner activators is thus governed by multiple dynamic equilibria. The latter should be judiciously adjusted to fine‐tune the catalytic properties of (thio)amides and organocatalysts, more generally. A fine blend of hydrogen bonds: New (thio)amidoindoles and (thio)amidobenzimidazoles catalyze the ring‐opening polymerization of lactide in the presence of a cocatalyst (see scheme). A detailed investigation of weak interactions showed that these catalysts are still active despite two undesired pathways, self‐aggregation, and hydrogen bonding between cocatalysts.