A1 Journal article (refereed)
Highly Syndiotactic or Isotactic Polyhydroxyalkanoates by Ligand-Controlled Yttrium-Catalyzed Stereoselective Ring-Opening Polymerization of Functional Racemic β-Lactones (2017)

Ligny, R., Hänninen, M. M., Guillaume, S. M., & Carpentier, J.-F. (2017). Highly Syndiotactic or Isotactic Polyhydroxyalkanoates by Ligand-Controlled Yttrium-Catalyzed Stereoselective Ring-Opening Polymerization of Functional Racemic β-Lactones. Angewandte Chemie International Edition, 56(35), 10388-10393. https://doi.org/10.1002/anie.201704283

JYU authors or editors

Publication details

All authors or editors: Ligny, Romain; Hänninen, Mikko M.; Guillaume, Sophie M.; Carpentier, Jean-Francois

Journal or series: Angewandte Chemie International Edition

ISSN: 1433-7851

eISSN: 1521-3773

Publication year: 2017

Volume: 56

Issue number: 35

Pages range: 10388–10393

Publisher: Wiley-VCH Verlag

Publication country: Germany

Publication language: English

DOI: https://doi.org/10.1002/anie.201704283

Publication open access: Not open

Publication channel open access: 

Abstract

Reported herein is the first stereoselective controlled ROP of a specific family of racemic functional β‐lactones, namely 4‐alkoxymethylene‐β‐propiolactones (BPLORs). This process is catalyzed by an yttrium complex stabilized by a nonchiral tetradentate amino alkoxy bisphenolate ligand {ONOOR′2}2−, which features both a good activity and a high degree of control over the molar masses of the resulting functional poly(3‐hydroxyalkanoate)s. A simple modification of the R′ substituents in ortho and para position on the ligand platform allows for a complete reversal from virtually pure syndioselectivity (Ps up to 0.91 with R′=cumyl) to very high isoselectivity (Pi up to 0.93 with R′=Cl), as supported by DFT insights. This is the first example of a highly isoselective ROP of a racemic chiral β‐lactone.

Keywords: polymers; esters; polymerisation; catalysis

Free keywords: ring-opening polymerization; stereoselective catalysis; Yttrium; beta-lactones

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Related projects

Ministry reporting: Yes

Reporting Year: 2017

JUFO rating: 3