Organocatalyzed Step-Growth Polymerization through Desymmetrization of Cyclic Anhydrides: Synthesis of Chiral Polyesters

Abstract : The polymerization of prochiral bis-anhydrides with diols catalyzed by a cinchona alkaloid was shown to provide chiral polyesters in good yields and with high levels of stereocontrol. The structures of the polyesters were determined by H-1 and C-13 NMR analyses, whereas their size was estimated by both size-exclusion chromatography (SEC) and MALDI-TOF mass spectrometry, which indicated that moderate degrees of polymerization were attained through this step-growth polymerization. The enantioselectivity of the process was evaluated by using chiral HPLC analysis of the bis-lactones resulting from a controlled chemoselective degradation of the polyesters. The best stereocontrol was reached for oligomers formed from bis-anhydride and diol monomers bearing rigid aromatic spacers between the reactive functional groups. In this case, average enantioselectivities were comparable to those observed during ring-opening of simple anhydrides with similar alcohols. In contrast, the use of more flexible spacers between reactive entities generally led to lower levels of stereocontrol.
Type de document :
Article dans une revue
Chemistry - A European Journal, Wiley-VCH Verlag, 2014, 20 (37), pp.11946-11953. <10.1002/chem.201402373 >
Domaine :
Liste complète des métadonnées

https://hal.archives-ouvertes.fr/hal-01366215
Contributeur : Catherine Roulinat <>
Soumis le : mercredi 14 septembre 2016 - 11:25:40
Dernière modification le : mercredi 12 octobre 2016 - 16:20:52

Identifiants

Collections

Citation

Anthony Martin, Frédéric Robert, Daniel Taton, Henri Cramail, Jean-Marc Vincent, et al.. Organocatalyzed Step-Growth Polymerization through Desymmetrization of Cyclic Anhydrides: Synthesis of Chiral Polyesters . Chemistry - A European Journal, Wiley-VCH Verlag, 2014, 20 (37), pp.11946-11953. <10.1002/chem.201402373 >. <hal-01366215>

Partager

Métriques

Consultations de la notice

41