Defining Stereochemistry in the Polymerization of Lactide by Aluminum Catalysts: Insights into the Dual-Stereocontrol Mechanism.

Aspects of the proposed pathway combining chain-end and enantiomorphic site control for the stereospecific polymerization of lactide (LA) were investigated through studies of aluminum complexes supported by enantiopure and racemic bipyrrolidine-based salan ligands, LigAlOBn and LigAlOBn. Spectroscopic analysis of stoichiometric initiation reactions and the definition of the stereochemistry of the selective formation of the "match" single-insertion products by X-ray crystallography led to key conclusions about the observed stereocontrol. Notably, it was determined to rely heavily on the preference for the trio of stereocenters around the metal to have a "match" formation (-ligand + -polymer), which works synergistically with the enantiomorphic site preference of the catalyst to ring-open next to a stereocenter of a monomer of the same chirality as that of the ligand, resulting in highly heterotactic or syndiotactic PLA from - or -LA, respectively.