CD-polymers as supramolecular, hydrophilic platforms for phototriggered multicomponent reactions in flow

CD-polymers as supramolecular, hydrophilic platforms for phototriggered multicomponent reactions in flow Marco Agnes,1 Claudia Felicia Mautone,1 Daniel Bisericaru,2 Milo Malanga,2 Szabolcs Beni,3 and Ilse Manet1 1Istituto per la Sintesi Organica e Fotoreattività (ISOF), CNR, Via Gobetti 101, 40129 Bologna, Italy 2CarboHyde Zrt., Berlini Str. 47–49, 1045, Budapest, Hungary 3Eötvös Loránd University (ELTE), Budapest, Hungary Presenting author email: [email protected] To meet the target set by the EU Green Deal and significantly decrease human impact on the planet by 2050, a strategy is to prioritize safe and sustainable-by-design (SSbD) materials for the development of less impacting catalytic processes in homogeneous aqueous environment. Cyclodextrin-polymers (CDPs) crosslinked with epichlorohydrin are able to i) organize in nanoparticles of diameter 20-50 nm, ii) increase the solubility of parent CDs up to 100 times and iii) co-solubilize more guests simultaneously, thanks to the assorted hydrophobic cavities and pockets.[1] Recently they have been shown to allow the photooxygenation of aromatic substrates at millimolar concentrations in water.[2] We further capitalized on the use of customized CDPs to perform highly efficient, photocatalytic reactions in homogeneous aqueous phase, in flow,[3] selected thiol-ene photo-additions and photooxygenations upon supramolecular loading of reactants into CDPs labelled with Photo-Active Ingredients (PAIs). Following a computational screening, the target reactions were optimized to achieve higher efficiency and selectivity in a photoreactor in flow. With our first results we endorse our forecast on CDPs as blockbuster SSbD matrix to perform homogeneous photocatalysis in greener conditions enabling unprecedented large scale chemical productions and boosting novel pharmacological and environmental applications. Figure 1. General strategy applying designed PAI-CDPs to the photo-induced conversion of organic substrates in homogeneous aqueous environment. Acknowledgements: HORIZON-MSCA-SE-01-01 2022 Bicyclos project #101130235; Fondazione di partecipazione ECOSISTER (ART-ER) Next Generation EU, PNRR-MUR. [1] M. Agnes et al., Macromol. Biosci. 2022, 22, 2200090 DOI: 10.1002/mabi.202200090; M. Agnes et al., J. Mater Chem. B 2024, 12, 7969-7976 DOI: 10.1039/D4TB01165A [2] M. Agnes et al., Chem. Eur. J. 2023, e202300511 DOI: 10.1002/chem.202300511 [3] M. Agnes et al., Eur. J. Org. Chem. 2024, 27, e202400861 DOI: 10.1002/ejoc.202400861 Do not write here