Stereoselectivity Control Interplay in Racemic Lactide Polymerization by Achiral Al‐Salen Complexes

The origin of stereocontrol in ring opening polymerization (ROP) of racemic lactide (rac‐LA) promoted by achiral aluminium‐based catalysts has been explained through DFT calculations combined with a molecular descriptor (%VBur) and the activation strain model (ASM‐NEDA) analysis. The proposed chain end control (CEC) model suggests that the ligand framework adopts a chiral configuration mimicking the enantiomorphic site control (ESC) while also incorporating control of the last inserted monomer unit. It is found that the ligand wrapping mode around the aluminium centre is dictated by the monomer configuration (R,R‐LA and S,S‐LA). A good correlation with experimental data is achieved only when accounting for the ligand dynamic features and its steric influences, as highlighted by %VBur steric maps and ASM‐NEDA analysis. Understanding the ESC and CEC interplay is an important target for obtaining stereoselective ROP polymerization for the synthesis of biodegradable materials with tailored properties. The stereoselectivity control in the racemic lactide polymerization process, mediated by achiral Al‐Salen complexes, has been rationalized using DFT calculations combined with activation strain model analysis and a steric molecular descriptor (%VBur). The primary features of both enantiomorphic site control and chain‐end control mechanisms are elucidated to explain the formation of isotactic [PDLA‐PLLA] stereoblocks.