Regio- and Stereoselective Lactone Polymerization: Divergent Effect of Catalyst Modification and Monomer Structure

Rusconi, Yolanda; D’Alterio, Massimo C.; Severson, Sarah M.; De Rosa, Claudio; Coates, Geoffrey W.; Talarico, Giovanni

doi:10.1021/acscatal.6c01584

Title: Regio- and Stereoselective Lactone Polymerization: Divergent Effect of Catalyst Modification and Monomer Structure

Journal Article · Wed Apr 22 00:00:00 UTC 2026 · ACS Catalysis

DOI: https://doi.org/10.1021/acscatal.6c01584 · OSTI ID:3374269

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Scuola Superiore Meridionale, Naples (Italy); University of Naples Federico II (Italy)
University of Naples Federico II (Italy)
Cornell University, Ithaca, NY (United States)

Selective ring-opening polymerization (ROP) of chiral lactones enables access to biodegradable polyesters with precisely controlled microstructures. Here, combined DFT modeling and experimental validation elucidate how fine-tuning of enantiopure SalBinam aluminum catalysts (through introduction of bromine atoms and tert-butyl groups, respectively, in ortho- and para-positions) modulates regio- and stereocontrol in the ROP of methyl glycolide (MeG) and lactide (LA). Computations reveal that regioselectivity in MeG polymerization arises mainly from steric repulsion, with a small contribution from weak stabilizing C-H···Br interactions that favor ring-opening at the glycolic site, consistent with the experimentally enhanced regioselectivity for (R)-MeG. In contrast, the same steric congestion at the ligand’s ortho positions destabilizes the key transition states in rac-LA polymerization, reducing the calculated stereoselectivity. Experiments confirm the predicted loss of stereocontrol, yielding nearly atactic PLA under standard conditions. Extension of the computational framework to rac-MeG polymerization promoted by racemic catalyst identified a low-barrier, stepwise polymer chain exchange pathway that rationalizes the experimentally observed syndiotacticity of poly(lactic-co-glycolic acid).

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Research Organization:: Cornell University, Ithaca, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-05ER15687

OSTI ID:: 3374269

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 10 Vol. 16; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Regio- and Stereoselective Lactone Polymerization: Divergent Effect of Catalyst Modification and Monomer Structure

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