Organocatalytic carbon dioxide fixation to epoxides by perfluorinated 1,3,5-triols catalysts - Aix-Marseille Université Accéder directement au contenu
Article Dans Une Revue Organic & Biomolecular Chemistry Année : 2020

Organocatalytic carbon dioxide fixation to epoxides by perfluorinated 1,3,5-triols catalysts

Résumé

In order to improve epoxides conversion to carbonates by fixation of CO 2 a new type of perfluorinated triol catalysts was developed. These simple acyclic scaffolds of enhanced acidity are efficient for catalysis through selective H-bonding activation of the epoxide. In combination with TBAI as co-catalyst, this useful transformation is performed under only 1 atmosphere of CO 2 and between 30 to 80°C. Both the 1,3,5-triol motif and the perfluorinated side chains are crucial in order to observe this epoxide opening under such mild conditions. In addition, the stereochemistry of the starting epoxide can efficiently be conserved during the carbonate formation. Designing catalysts with improved activity and/or selectivity is at the heart of modern chemical research. For this purpose, chemists must identify new scaffolds possessing optimized functions and geometry for maximized efficiency in useful catalytic transformations. The massive amount of CO 2 generated in the last decades have pushed chemists to take advantage of this chemical as an inexpensive and abundant raw material. In this context, CO 2 can be used in a circular economy platform either as an energy source through its transformation to fuels such as methanol, or as a source of bulk chemical commodities. 1 Among these, cyclic carbonates of great industrial utility can be generated by a fascinating epoxide opening with CO 2 (Scheme 1a). These carbonates can be used as alternative solvents or for the production of plastics, pharmaceuticals and other fine chemicals. 2 Given this industrial interest, development of new tools enabling the optimum reuse of CO 2 for the preparation of these higher value chemicals is vital. In order to activate CO 2 towards its appropriate fixation on epoxides, tremendous efforts have been achieved to improve reaction efficiency and decrease costs and hazards. 3 Progress in that direction notably imply introduction of inexpensive organocatalysts of improved catalytic activity and avoiding unnecessary toxic metals. 4 However, despite the design of better catalysts, the challenge is to introduce alternative catalytic scaffolds enabling CO 2 fixation under exquisitely mild conditions. Most notably, simple catalytic structures enabling CO 2 activation and fixation at temperatures below 100°C and atmospheric pressure are highly desirable for greener industrial processes and still constitutes a challenge. 5 Given the lack of activity of numerous organocatalysts, a number of systems combining Hydrogen Bond Donor catalysts (HBD) and a qua-ternary ammonium salt co-catalyst have been developed. The nucleophilic counter anion of the salt acts as a temporary Scheme 1 Organocatalytic epoxide opening with CO 2 and proposed catalysts. † Electronic supplementary information (ESI) available. See

Domaines

Chimie organique
Fichier principal
Vignette du fichier
Pub_AQ_13 - copie.pdf (1.4 Mo) Télécharger le fichier
Origine : Fichiers produits par l'(les) auteur(s)
Loading...

Dates et versions

hal-02568127 , version 1 (08-05-2020)

Identifiants

Citer

Céline Sperandio, Jean Rodriguez, Adrien Quintard. Organocatalytic carbon dioxide fixation to epoxides by perfluorinated 1,3,5-triols catalysts. Organic & Biomolecular Chemistry, 2020, 18 (14), pp.2637-2640. ⟨10.1039/d0ob00402b⟩. ⟨hal-02568127⟩

Relations

19 Consultations
32 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More