Phosphonated furan-functionalized poly(ethylene oxide)s using orthogonal click chemistries: synthesis and Diels–Alder reactivity

Abstract

The synthesis and the reactivity in Diels-Alder and retro Diels-Alder (DA/rDA) reactions of a series of novel phosphonated furan-functionalized PEO monomethyl ethers were investigated. Dimethylphosphonate-terminated furan-functionalized PEO monomethyl ethers and their phosphonic acid-terminated derivatives have been successfully prepared by using a combination of click copper-catalyzed 1,3dipolar cycloaddition and Kabachnik-Fields reactions. Influence of both the substitution pattern of the furan ring and the solvent onto the DA/rDA process were investigated. It was found that the 3-substituted furan is the more reactive and that water facilitates both the DA and the rDA reactions, while maintaining the polymeric structure intact. The results demonstrate the potential of such structures for dynamic covalent applications and controlled drug delivery systems such as thermoreversible linkage of biological entities onto metallic nanoparticles.Scheme 1 The concept of magnetically stimulated rDA reaction using IONPs. † Electronic supplementary information (ESI) available: Detailed experimental procedures and NMR spectra. See a Determined by 1 H NMR spectroscopy by comparing the peak areas of the CH-O groups of oxanorbornene at δ = 5.13-5.39 ppm and the methylene protons of the PEO in α of the triazole ring at δ = 4.52 ppm. PaperPolymer ChemistryPolym. Chem. This journal is

Diels–Alder Cycloadditions of Bio-Derived Furans with Maleimides as a Sustainable «Click» Approach towards Molecular, Macromolecular and Hybrid Systems

“…However, many important areas, including the development of room-temperature self-remendable polymers, application of acceptor-substituted furans for the synthesis of fine chemicals and materials, need further study. Moreover, new, industrially relevant technologies towards the pro- Besides thermal initiation, rDA reaction in CANs can be driven by other stimuli, such as light [107], mechanical [138] or magnetic force [139]. Light-responsive CANs based on a photocontrolled DA reaction could be obtained by the introduction of the fluorescent fragment into diene or dienophile [107,140,141].…”

“…A comparison of the rate of coupling for some fmDA adducts has shown that the efficiency of thermal and mechanical activation is not equal and depends on the regio-and stereo structure of the adducts: some diastereomers can be mechano-resistant due to misalignment of the dynamic DA bonds with the force vector providing ineffective mechanochemical interactions [147]. Besides thermal initiation, rDA reaction in CANs can be driven by other stimuli, such as light [107], mechanical [138] or magnetic force [139]. Light-responsive CANs based on a photocontrolled DA reaction could be obtained by the introduction of the fluorescent fragment into diene or dienophile [107,140,141].…”

“…dendrimers [131] R = NH 2 Epoxy resins [132,133] Processes 2021, 9, x FOR PEER REVIEW 13 of 20 Besides thermal initiation, rDA reaction in CANs can be driven by other stimuli, such as light [107], mechanical [138] or magnetic force [139]. Light-responsive CANs based on a photocontrolled DA reaction could be obtained by the introduction of the fluorescent fragment into diene or dienophile [107,140,141].…”