Cited by 713biodegradable polymer synthesis and propertiesAsymmetric Synthesis and CatalysisOrganometallic Complex Synthesis and Catalysis

Stereochemistry of Lactide Polymerization with Chiral Catalysts: New Opportunities for Stereocontrol Using Polymer Exchange Mechanisms

Ovitt, Tina M., Coates, Geoffrey W.·2002·Journal of the American Chemical Society

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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Crossref · 10.1021/ja012052+

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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.”

    From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [303]

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Authors
Ovitt, T. M., & Coates, G. W.
Affiliations
Cornell University (US)
Venue
Journal of the American Chemical Society
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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