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Cited by 22biodegradable polymer synthesis and propertiesPolymer crystallization and propertiesAsymmetric Synthesis and Catalysis

Stereodivergent transformation of a natural polyester to enantiopure PHAs

Tian, Jun-Jie, Li, Ruirui, Quinn, Ethan C., Nam, Jiyun, Chokkapu, Eswara Rao, Zhang, Zhen, Zhou, Li, Gowda, Ravikumar R. +1 more·2025·Nature
DOI 10.1038/s41586-025-09220-7
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Abstract

Natural chiral polymers, such as DNA, proteins, cellulose and poly[(R)-3-hydroxybutyrate] ((R)-P3HB), are prevalent in their enantiopure forms 1,2. Existing methods to synthesize enantiopure polymers focus on enantiospecific polymerization, in which only one specific enantiomer is obtained from the corresponding chiral monomer 3-6. Here we introduce a catalytic stereodivergent synthetic strategy to access all enantiopure di-isotactic poly(3-hydroxyalkanoate) (PHA) diastereomers from bacterial (R)-P3HB as the single chiral source. A series of enantiopure (R,R)-α-alkylated-β-butyrolactones are obtained from (R)-P3HB and then subjected to the catalyst-controlled diastereodivergent ring-opening polymerization (ROP) to enantiopure di-isotactic α-alkylated PHAs. Metal-catalysed coordination-insertion ROP results in threo-(R,R)-di-isotactic PHAs with chiral retention, whereas anionic ROP catalysed by an organic superbase produces erythro-(R,S)-di-isotactic PHAs with chiral inversion, achieving precision di-isotactic PHAs with exclusive regio- and stereoregularity. This strategy has also enabled the stereodivergent synthesis of all four [(R,R), (S,S), (R,S) and (S,R)] stereoisomers of α,α-dialkylated PHAs from (R)-P3HB, which can be depolymerized to chiral α,α-dialkylated-β-butyrolactones with high stereoselectivity. Overall, this catalyst-controlled regio- and stereoselective, stereodivergent synthetic methodology provides access to 16 enantiopure stereoisomers of α(α)-(di)substituted PHAs and enables the stereochemistry-defined structure-property relationship study of the di-isotactic PHAs, providing insights into the effects of main-chain stereoconfigurations and alkyl side chains on their thermal properties, melt processability, mechanical performance and supramolecular stereocomplexation.

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Crossref · 10.1038/s41586-025-09220-7

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  • Physical blending of enantiomeric chiral polyesters in a stoichiometric ratio is a well-established strategy for constructing highly crystalline stereocomplex (sc) materials, which often exhibit higher Tm values and faster crystallization rates compared to their individual enantiomeric counterparts.

    “Physical blending of enantiomeric chiral polyesters in a stoichiometric ratio is a well-established strategy for constructing highly crystalline stereocomplex ( sc ) materials, which often exhibit higher T m values and faster crystallization rates compared to their individual enantiomeric counterparts [51-55].”

    From Functional and Network PHAs via Stereoselective Polymerization and Tailored Post‐Transformation (2026) · cites this paper as [55]

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Authors
Tian, J.-J., Li, R., Quinn, E. C., Nam, J., Chokkapu, E. R., Zhang, Z., Zhou, L., Gowda, R. R., & Chen, E. Y.-X.
Affiliations
Colorado State University (US)
Corresponding author
Chen, Eugene Y.-X.
ORCID
Venue
Nature
Publisher
Springer Science and Business Media LLC
Published
2025-07-02
Volume
643
Issue
8073
Pages
967-974
ISSN
  • 0028-0836 (ISSN-L)
  • 1476-4687
DOI
10.1038/s41586-025-09220-7
OpenAlex
W4411932254
Cited by
21
References
44
Citations by year
2026: 14 · 2025: 7
FWCI
4.44
Type
journal article
Language
en
Open access
closed
Licence
Locations
  • Nature (publishedVersion)
  • PubMed (publishedVersion)
Topics
  • Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
  • Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
  • Physical Sciences › Chemistry › Organic Chemistry › Asymmetric Synthesis and Catalysis
Keywords
polyhydroxyalkanoates, stereodivergent synthesis, poly[(R)-3-hydroxybutyrate], ring-opening polymerization, coordination-insertion polymerization, anionic polymerization, β-butyrolactone, depolymerization, stereoselective synthesis, chiral inversion, stereocomplexation, structure-property relationships
MeSH terms
Alkylation, Catalysis, Polyesters, Stereoisomerism, Polyhydroxyalkanoates, Polymerization

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