Stereochemistry of Lactide Polymerization with Chiral Catalysts: New Opportunities for Stereocontrol Using Polymer Exchange Mechanisms
Abstract
The synthesis of chiral aluminum and yttrium alkoxides and their application for lactide polymerization are reported. The complexes (SalBinap)MOR [4, M = Al, R = (i)Pr; 5, M = Y, R = (CH(2))(2)NMe(2)] are synthesized by reacting the ligand (SalBinap)H(2) [2,2'-[(1,1'-binaphthalene)-2,2'-diylbis(nitrilomethylidyne)]bisphenol] with the appropriate metal trisalkoxide. While enantiomerically pure yttrium complex 5 did not effect stereocontrol in the polymerization of either meso- or rac-lactide, homochiral 4 was found to exhibit excellent stereocontrol in a range of lactide polymerizations. Enantiomerically pure 4 polymerizes meso-lactide to syndiotactic poly(lactic acid) (PLA), while rac-4 polymerizes meso- and rac-lactide to heterotactic and isotactic stereoblock PLA, respectively. On the basis of the absolute stereochemistry of ring-opening of meso-lactide using (R)-4, a polymer exchange mechanism is proposed to account for the PLA microstructures resulting from rac-4.
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Aluminum complexes supported by SALEN-type ligands are some of the most stereoselective catalysts for the ROP of racemic LA, but their low reactivities limit their applicability.
“Aluminum complexes supported by SALEN-type ligands [301][302][303][304][305][306][307][308][309] are some of the most stereoselective catalysts for the ROP of racemic LA but their low reactivities (typical reaction conditions: Al loading >1 mol%, 70-130 °C, and long reaction time) limit their applicability.”
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- Authors
- Ovitt, T. M., & Coates, G. W.
- Affiliations
- Cornell University (US)
- ORCID
- Coates, Geoffrey W.
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2002-01-26
- Volume
- 124
- Issue
- 7
- Pages
- 1316-1326
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W2000855711
- Cited by
- 713
- References
- 25
- Citations by year
- 2026: 14 · 2025: 19 · 2024: 23 · 2023: 16 · 2022: 19 · 2021: 18 · 2020: 22 · 2019: 25 · 2018: 26 · 2017: 43 · 2016: 33 · 2015: 54 · 2014: 55 · 2013: 47 · 2012: 54
- FWCI
- 11.99
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Journal of the American Chemical Society (publishedVersion)
- PubMed (publishedVersion)
- Topics
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Chemistry › Organic Chemistry › Asymmetric Synthesis and Catalysis
- Physical Sciences › Chemistry › Organic Chemistry › Organometallic Complex Synthesis and Catalysis
- Keywords
- lactide polymerization, meso-lactide, rac-lactide, enantioselective polymerization, stereoblock polymers
- MeSH terms
- Aluminum, Catalysis, Magnetic Resonance Spectroscopy, Organometallic Compounds, Polyesters, Stereoisomerism, Ytterbium, Crystallography, X-Ray
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