The reaction mechanism for the organocatalytic ring-opening polymerization of L-lactide using a guanidine-based catalyst: Hydrogen-bonded or covalently bound?

We have investigated two alternative mechanisms for the ring-opening polymerization of L-lactide using a guanidine-based catalyst, the first involving acetyl transfer to the catalyst, and the second involving only hydrogen bonding to the catalyst. Using computational chemistry methods, we show that the hydrogen bonding pathway is considerably preferred over the acetyl transfer pathway and that this is consistent with experimental information. © 2008 American Chemical Society.