1. Mechanistic Insight into the Stereochemical Control of Lactide Polymerization by Salan–Aluminum Catalysts
- Author
-
Israel Goldberg, Konstantin Press, and Moshe Kol
- Subjects
chemistry.chemical_classification ,Lactide ,Ligand ,Diastereomer ,General Medicine ,General Chemistry ,Catalysis ,chemistry.chemical_compound ,chemistry ,Polymerization ,Benzyl alcohol ,Tacticity ,Organic chemistry ,Alkyl - Abstract
Alkyl aluminum complexes of chiral salan ligands assembled around the 2,2'-bipyrrolidine core form as single diastereomers that have identical configurations of the N donors. Active catalysts for the polymerization of lactide were formed upon the addition of benzyl alcohol. Polymeryl exchange between enantiomorphous aluminum species had a dramatic effect on the tacticity of the poly(lactic acid) (PLA) in the polymerization of racemic lactide (rac-LA): The enantiomerically pure catalyst of the nonsubstituted salan ligand led to isotactic PLA, and the racemic catalyst exhibited lower stereocontrol. The enantiomerically pure catalyst of the chloro-substituted salan ligand led to PLA with a slight tendency toward heterotacticity, whereas the racemic catalyst led to PLA of almost perfect heterotacticity following an insertion/auto-inhibition/exchange mechanism.
- Published
- 2015