Post-Modification of Copolymers Obtained by ATRP for an Application in Heterogeneous Asymmetric Salen Catalysis

Copolymers are valuable supports for obtaining heterogeneous catalysts that allow their recycling and therefore substantial savings, particularly in the field of asymmetric catalysis. This contribution reports the use of two comonomers: Azido-3-propylmethacrylate (AZMA) bearing a reactive azide func...

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Published in:Molecules (Basel, Switzerland) Switzerland), 2022-07, Vol.27 (14), p.4654
Main Authors: Bakangura, Erigene, Roger, Philippe, Soares, Rafaela S. B., Mellah, Mohamed, Barroca-Aubry, Nadine, Gouget-Laemmel, Anne-Chantal, Ozanam, François, Costa, Ludovic, Baltaze, Jean-Pierre, Schulz, Emmanuelle
Format: Article
Language:English
Subjects:
Asymmetry
ATRP
Bimetals
Carbon
Catalysis
Catalysts
Chemical activity
Chemical Sciences
Chromium
Coordination chemistry
Copolymerization
Copolymers
Efficiency
Enantiomers
heterogeneous asymmetric catalysis
Organic chemistry
Polymerization
Polymers
post-modification
Ring opening
salen
Selectivity
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Summary:Copolymers are valuable supports for obtaining heterogeneous catalysts that allow their recycling and therefore substantial savings, particularly in the field of asymmetric catalysis. This contribution reports the use of two comonomers: Azido-3-propylmethacrylate (AZMA) bearing a reactive azide function was associated with 2-methoxyethyl methacrylate (MEMA), used as a spacer, for the ATRP synthesis of copolymers, and then post-functionalized with a propargyl chromium salen complex. The controlled homopolymerization of MEMA by ATRP was firstly described and proved to be more controlled in molar mass than that of AZMA for conversions up to 63%. The ATRP copolymerization of both monomers made it possible to control the molar masses and the composition, with nevertheless a slight increase in the dispersity (from 1.05 to 1.3) when the incorporation ratio of AZMA increased from 10 to 50 mol%. These copolymers were post-functionalized with chromium salen units by click chemistry and their activity was evaluated in the asymmetric ring opening of cyclohexene oxide with trimethylsilyl azide. At an equal catalytic ratio, a significant increase in enantioselectivity was obtained by using the copolymer containing the largest part of salen units, probably allowing, in this case, the more favorable bimetallic activation of both the engaged nucleophile and electrophile. Moreover, the catalytic polymer was recovered by simple filtration and re-engaged in subsequent catalytic runs, up to seven times, without loss of activity or selectivity.
ISSN:1420-3049
1420-3049
DOI:10.3390/molecules27144654