Cited by 93biodegradable polymer synthesis and propertiesAsymmetric Synthesis and CatalysisAdvanced Polymer Synthesis and Characterization

Enantioselective Ring-Opening Polymerization of rac-Lactide Dictated by Densely Substituted Amino Acids

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Sanchez-Sanchez, Ana, Rivilla, Ivan, Agirre, Maddalen, Basterretxea, Andere, Etxeberria, Agustin, Veloso, Antonio, Sardon, Haritz, Mecerreyes, David +1 more·2017·Journal of the American Chemical Society

Abstract

Organocatalysis is becoming an important tool in polymer science because of its versatility and specificity. To date a limited number of organic catalysts have demonstrated the ability to promote stereocontrolled polymerizations. In this work we report one of the first examples of chirality transfer from a catalyst to a polymer in the organocatalyzed ring-opening polymerization (ROP) of rac -lactide ( rac -LA). We have polymerized rac -LA using the diastereomeric densely substituted amino acids (2 S,3 R,4 S,5 S )-1-methyl-4-nitro-3,5-diphenylpyrrolidine-2-carboxylic acid ( endo - 6 ) and (2 S,3 S,4 R,5 S )-1-methyl-4-nitro-3,5-diphenylpyrrolidine-2-carboxylic acid ( exo - 6 ), combined with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as a cocatalyst. Both diastereoisomers not only showed the ability to synthesize enriched isotactic polylactide with a P m higher than 0.90 at room temperature but also were able to preferentially promote the polymerization of one of the isomers ( l or d ) with respect to the other. Thus, exo - 6 preferentially polymerized l -lactide, whereas endo - 6 preferred d -lactide as the substrate. Density functional theory calculations were conducted to investigate the origins of this unique stereocontrol in the polymerization, providing mechanistic insight and explaining why the chirality of the catalyst is able to define the stereochemistry of the monomer insertion.

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Crossref · 10.1021/jacs.6b13080

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  • exo-PRO exhibited a strong preference for L-LA and the ROP of rac-LA by this catalyst at 50% conversion generates highly isotactic PLAs with Pm up to 0.96 at 25 °C.

    “exo-PRO exhibited a strong preference for L-LA and the ROP of rac-LA by this catalyst at 50% conversion generates a highly isotactic PLAs with Pm up to 0.96 at 25 °C.342”

    From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [342]

  • Mecerreyes and Cossío found that a cocatalytic system consisting of a densely substituted proline and DBU was able to kinetically resolve racemic lactide.

    “Mecerreyes and Cossío found that a cocatalytic system consisted of a densely substituted proline (PRO, Figure 9) and DBU was able to kinetically resolve racemic lactide.”

    From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [342]

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Authors
Sanchez-Sanchez, A., Rivilla, I., Agirre, M., Basterretxea, A., Etxeberria, A., Veloso, A., Sardon, H., Mecerreyes, D., & Cossío, F. P.
Affiliations
  • POLYMAT, University of the Basque Country UPV/EHU, Joxe Mari Korta Center, Avda. Tolosa 72, 20018 Donostia/San Sebastian, Spain
  • Departamento de Química Orgánica I and Instituto de Innovación en Química Avanzada (ORFEO−CINQA), University of the Basque Country UPV/EHU, P° Manuel Lardizabal 3, 20018 Donostia/San Sebastian, Spain
  • University of the Basque Country (ES)
  • Department of Polymer Science and Technology, Institute of Polymer Materials, University of the Basque Country UPV/EHU, P° Manuel Lardizabal 3, 20018 Donostia/San Sebastian, Spain
  • Ikerbasque (ES)
Corresponding author
  • Mecerreyes, David
  • Cossío, Fernando P.
Venue
Journal of the American Chemical Society
Published
2017-03-22
Volume
139
Issue
13
Pages
4805-4814
ISSN
  • 0002-7863 (ISSN-L)
  • 1520-5126
OpenAlex
W2592144576
Cited by
93
References
50
Citations by year
2026: 3 · 2025: 10 · 2024: 11 · 2023: 9 · 2022: 10 · 2021: 7 · 2020: 9 · 2019: 13 · 2018: 16 · 2017: 5
FWCI
4.23
Type
journal article
Language
en
Open access
Licence
other-oa
Locations
  • Journal of the American Chemical Society (publishedVersion)
  • PubMed (publishedVersion)
  • Communities in ADDI (Universidad del Pais Vasco) (submittedVersion, other-oa)
  • Communities in ADDI (University of the Basque Country) (submittedVersion, other-oa)
  • LA Referencia (Red Federada de Repositorios Institucionales de Publicaciones Científicas) (submittedVersion)
  • Hispana (submittedVersion, other-oa)
Funders
  • European Commission (EJD 642671, FDI 16507)
  • Ministerio de Econom?a y Competitividad (CTQ2016-80375-P, CTQ2016-81797-REDC)
  • Eusko Jaurlaritza (IT618-13, IT673-13)
  • Euskal Herriko Unibertsitatea (UFI 11/22 QOSYC)
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 › Advanced Polymer Synthesis and Characterization
Keywords
rac-lactide, organocatalysis, chirality transfer, stereoselective polymerization, polymerization mechanism, density functional theory
MeSH terms
Amino Acids, Dioxanes, Polyesters, Stereoisomerism, Molecular Structure, Polymerization

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