Thiourea-Based Bifunctional Organocatalysis:  Supramolecular Recognition for Living Polymerization

A versatile, metal-free, organocatalytic approach to the living ring-opening polymerization of lactide using a bifunctional thiourea−tertiary amine catalyst is described. Mild and highly selective polymerization conditions produced poly(lactides) with predictable molecular weights and extremely narrow polydispersities (∼1.05), characteristic of a living polymerization. The extraordinary selectivity of this catalyst system for polymerization relative to transesterification is remarkably unusual. The low polydispersities and exceptional control observed are a consequence of selective transesterification of lactide relative to the open chain esters. Presumably, the ring strain of lactide provides both a driving force for the polymerization and a kinetic preference for polymerization relative to transesterification with catalyst. We postulate that the initiating/propagating alcohol is activated by acid−base interaction with the tertiary amine moiety and the carbonyl of the lactide monomer is simultaneously activated by hydrogen bonding to the thiourea moiety of the catalyst.