Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 16, Issue 14, Pages 4196-4205Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200902912
Keywords
hydrogen bonds; lactides; organocatalysis; partner catalysts; ring-opening polymerization
Categories
Funding
- Agence Nationale de la Recherche (ANR)
- Chimie des Procedes et du Developpement Durable Program [ANR-07-CP2D-15]
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The mechanism of the ring-opening polymerization (ROP) of lactide catalyzed by two partner hydrogen-bonding organocatalysts was explored. New amidoindoles 4a,c, thioamidoindoles 4b,d, amidobenzimidazoles 5a,c, and thioamidobenzimidazoles 5b,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 3a or 3b, which activates the growing polymer chain through hydrogen-bonding. Reactions were conducted in 2-24 h at 20 degrees 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.
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