Zwitterionic Ring Opening Polymerization with Isothioureas

Bicyclic isothioureas 1 and 2 mediate controlled ring opening polymerizations (ROP) of lactides in the absence of protic initiators to afford high molecular weight polylactides (PLA) with narrow polydispersities. The cyclic structure of the resulting PLA was determined by dilute solution viscosity measurement and MALDI-TOF mass spectrometry. Compared to DBU initiator, isothioureas are more selective for producing cyclic PLA without appreciable linear contaminants. Mechanistic studies involving acyl amidinium support our hypothesis that DBU-initiated ZROP generates linear chains from a ketene aminal intermediate.