Acyclic guanidines as organic catalysts for living polymerization of lactide

We describe a facile route to structurally diverse guanidinium organic catalysts by reaction of carbodiimides with secondary amines. The efficacy of these catalysts for the living ring-opening polymerization (ROP) of lactide was demonstrated including predictable molecular weights and end-group fidelity. Theoretical studies indicate that the acyclic guanidines are less basic than 1, 5, 7-triazabicyclo[4.4.0]dec-5-ene (TBD), but as for the more active TBD, they catalyze ring opening by activation of the alcohol and by stabilizing the resultant tetrahedral intermediates through hydrogen bonding. These results demonstrate that weak secondary interactions are an important concept for controlled polymerization. © 2010 American Chemical Society.