Aminobisphosphonate Polymers via RAFT and a Multicomponent Kabachnik–Fields Reaction

The phosphonic acid functional group, which is characterized by a phosphorus atom bonded to three oxygen atoms (two hydroxy groups and one P=O double bond) and one carbon atom, is employed for many applications due to its structural analogy with the phosphate moiety or to its coordination or supramolecular properties. Phosphonic acids were used for their bioactive properties (drug, pro-drug), for bone targeting, for the design of supramolecular or hybrid materials, for the functionalization of surfaces, for analytical purposes, for medical imaging or as phosphoantigen. These applications are covering a large panel of research fields including chemistry, biology and physics thus making the synthesis of phosphonic acids a determinant question for numerous research projects. This review gives, first, an overview of the different fields of application of phosphonic acids that are illustrated with studies mainly selected over the last 20 years. Further, this review reports the different methods that can be used for the synthesis of phosphonic acids from dialkyl or diaryl phosphonate, from dichlorophosphine or dichlorophosphine oxide, from phosphonodiamide, or by oxidation of phosphinic acid. Direct methods that make use of phosphorous acid (H3PO3) and that produce a phosphonic acid functional group simultaneously to the formation of the P–C bond, are also surveyed. Among all these methods, the dealkylation of dialkyl phosphonates under either acidic conditions (HCl) or using the McKenna procedure (a two-step reaction that makes use of bromotrimethylsilane followed by methanolysis) constitute the best methods to prepare phosphonic acids.

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“…31 ). However, the conditions of the Moedritzer–Irani reaction induced the hydrolysis of the polymers side chains [ 226 ].…”

Section: Reviewmentioning

confidence: 99%

Phosphonic acid: preparation and applications

Sevrain¹,

Berchel²,

Couthon³

et al. 2017

Beilstein J. Org. Chem.

147

103

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“…Commonly used heavy metals, such as plutonium and uranium, exhibit both chemical and radiological toxicities. To address these concerns, bisphosphonate‐ and aminobisphosphonate‐based polymers have been investigated as multidentate materials to chelate heavy metals . Lahrouch et al recently demonstrated the affinity of polyethyleneimine methylphosphonate (PEI‐MP) (Fig.…”

Section: Polymer Chelation Therapymentioning

confidence: 99%

Polymer sequestrants for biological and environmental applications

Archer

Hall

Thompson

et al. 2019

Polymer International

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Toxic contaminates have profound consequences on both health and the environment. Consequently, effective approaches for addressing the effects of these toxicants are paramount. Here, we review recent progress in developing polymeric sequestrants for biological toxins, heavy metals and organic micropollutants. Polymers have several advantages as sequestration materials, including relatively low cost and high affinity for target compounds. As a result a number of polymer-based toxin-mitigation applications have been investigated. Naturally occurring toxins may be neutralized with polymers capable of binding and eliminating them from the body. Heavy metal contamination from mining operations, energy and industrial sources may also be mitigated with appropriate chelating polymers, both for environmental remediation and in chelation therapy for metal poisoning. Micropollutants such as pesticides from agriculture and polycyclic aromatic hydrocarbons from combustion processes may also be isolated using polymeric materials. Each of these applications illustrates the capabilities of polymers for eliminating toxic contaminants, thereby facilitating greater health and sustainability.

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“…Examples of such MCRs include the Passerini, Ugi, Biginelli, Hantzsch, Kabachnik–Fields (KF), and Mannich reactions. [ 15–32 ] MCRs are suitable for the preparation of polymer antioxidants for several reasons. Some antioxidative groups such as phenol are compatible with many MCRs and can be easily introduced into polymer chains without losing their antioxidative ability.…”

Section: Introductionmentioning

confidence: 99%

“…[ 37–40 ] However, the KF reaction has been used only recently in polymer chemistry. [ 26,28,29,41–45 ] Some new polymers have been prepared via the KF reaction and used as flame‐resistant and antibacterial materials. [ 43–45 ] However, the preparation of antioxidant polymers via the KF reaction has not been reported.…”

Section: Introductionmentioning

confidence: 99%

Antioxidant Polymers via the Kabachnik‐Fields Reaction to Control Cellular Oxidative Stress

Liu

Tian

et al. 2020

Macromolecular Bioscience

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Small molecular antioxidants are almost ineffective in regulating harmful oxidative stress in vivo because of their poor bioavailability. Polymer antioxidants are a promising alternative to address this issue, but their laborious synthetic routes limit their development. In this study, aliphatic and aromatic aldehydes are used to synthesize a family of polymers containing different α‐aminophosphonate pendant groups via a facile one‐pot method that combines the Kabachnik–Fields (KF) reaction and free radical polymerization. The structure–property relationship study of these polymers reveals the KF moieties in polymer structures confer radical scavenging ability on polymers. The radical scavenging ability and cytotoxicity of these polymers are evaluated in a stepwise manner to identify a biocompatible polymer antioxidant that can effectively protect the cells from H2O2‐induced oxidative damage. This is the first attempt to develop antioxidative polymers by the KF reaction. It highlights the feasibility of synthesizing new functional polymers using multicomponent reactions, which has important implications for organic and polymer chemistry.

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Aminobisphosphonate Polymers via RAFT and a Multicomponent Kabachnik–Fields Reaction

Cited by 40 publications

References 52 publications

Phosphonic acid: preparation and applications

Phosphonic acid: preparation and applications

Polymer sequestrants for biological and environmental applications

Antioxidant Polymers via the Kabachnik‐Fields Reaction to Control Cellular Oxidative Stress

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