Synthesis of α,ω-heterotelechelic PVP for bioconjugation, via a one-pot orthogonal end-group modification procedure

Reader, Paul W.; Pfukwa, Rueben; Jokonya, Simbarashe; Arnott, Gareth E.; Klumperman, Bert

doi:10.1039/c6py01296e

Cited by 17 publications

(23 citation statements)

References 40 publications

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“…For instance, a heterotelechelic a-aldehyde, o-thiol polyvinylpyrrolidone (PVP) synthesized by RAFT polymerization was functionalized with glycine-D,L-serine and phenyl acrylate, respectively. 54 Also, by starting from difunctional trithiocarbonate RAFT agents bearing aminooxy groups or pyridyl disulfide (PDS) groups (Fig. 8a and b), corresponding homotelechelic poly[oligo(ethylene glycol)methyl ether acrylate] (POEGA) polymers were successfully prepared ( Fig.…”

Section: Peptide/protein Conjugationmentioning

confidence: 99%

Telechelic polymers from reversible-deactivation radical polymerization for biomedical applications

2018

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Section: Peptide/protein Conjugationmentioning

confidence: 99%

Telechelic polymers from reversible-deactivation radical polymerization for biomedical applications

2018

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“…As such, it can be readily statistically copolymerized with comonomers such as vinyl acetate or acrylics. However, its copolymerization with methacrylics or styrene is more problematic, with strongly non-ideal behavior typically being observed. − There are a number of literature reports of the reversible addition–fragmentation chain transfer (RAFT) polymerization of NVP using xanthates or dithiocarbamates. − However, control is usually inferior to that achieved for (meth)acrylic monomers under optimized conditions, particularly for polymerizations performed in aqueous solution. − For example, Guinaudeau et al reported the successful RAFT/MADIX aqueous polymerization of PNVP-based double-hydrophilic diblock copolymers by employing redox initiation at ambient temperature. , Using ascorbic acid led to the formation of N -(α-hydroxyethyl)pyrrolidone in acidic solution, but switching to sodium sulfite under mildly alkaline conditions (pH 9) prevented generation of this unwanted side product. Under the latter optimized conditions, relatively good control was achieved for the RAFT homopolymerization of NVP ( M w / M n < 1.20).…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Well-Defined Pyrrolidone-Based Homopolymers and Stimulus-Responsive Diblock Copolymers via RAFT Aqueous Solution Polymerization of 2-(N-Acryloyloxy)ethylpyrrolidone

et al. 2018

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Poly(N-vinylpyrrolidone) (PNVP) is a well-known, highly polar, nonionic water-soluble polymer. However, N-vinylpyrrolidone (NVP) usually exhibits strongly non-ideal behavior when copolymerized with methacrylic or styrenic monomers. Moreover, NVP is not particularly well-controlled under living radical polymerization conditions. For these reasons, alternative pyrrolidone-based monomers have been investigated. For example, the reversible addition–fragmentation chain transfer (RAFT) polymerization of 2-(N-methacryloyloxy)ethylpyrrolidone (NMEP) has been recently investigated using various polymerization formulations. However, PNMEP homopolymers are significantly less hydrophilic than PNVP and exhibit inverse temperature solubility in aqueous solution. In the present work, we studied the RAFT aqueous solution polymerization of 2-(N-acryloyloxy)ethylpyrrolidone (NAEP) using either AIBN at 70 °C or a low-temperature redox initiator at 30 °C. PNAEP homopolymers are obtained in high yield (>99%) with good control (Mw/Mn < 1.20) for target degrees of polymerization (DP) of up to 400 using the latter initiator, which produced relatively fast rates of polymerization. However, targeting DPs above 400 led to lower NAEP conversions and broader molecular weight distributions. 2-Hydroxyethyl acrylate (HEA) and oligo(ethylene glycol) methyl ether acrylate (OEGA) were chain-extended using a PNAEPx macro-CTA via RAFT aqueous solution polymerization, yielding double-hydrophilic acrylic diblock copolymers with high conversions (>99%) and good control (Mw/Mn < 1.31). In addition, a PNAEP95 macro-CTA was chain-extended via RAFT aqueous solution polymerization of N-isopropylacrylamide (NIPAM) at 22 °C. Dynamic light scattering (DLS) analysis indicated that heating above the lower critical solution temperature of PNIPAM led to so-called “anomalous micellization” at 35 °C and the formation of near-monodisperse spherical micelles at 40 °C. Finally, 2-(diethylamino)ethyl methacrylate (DEA) was polymerized using an N-morpholine-functionalized trithiocarbonate-based RAFT chain transfer agent and subsequently chain-extended using NAEP to form a novel pH-responsive diblock copolymer. Above the pKa of PDEA (∼7.3), DLS and 1H NMR studies indicated the formation of well-defined PDEA-core spherical micelles.

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“…At last, it was purified by chromatography (PE/EtOAc, 2:1, Rf = 0. Compound 4 (16.1 mg, 0.05 mmol), oseltamivir derivative 5 (16.9 mg, 0.05 mmol, the preparation according to previous reports) 15 and CuI (0.9 mg, 0.005 mmol) were charged into a Schlenk tube, and DMF (1 mL) was added under nitrogen. The reaction mixture was stirred at 60 o C for 14 h. At ambient temperature, H2O (2.5 mL) was added and the compound was extracted with EtOAc (15 mL × 3).…”

Section: '5(2'h)-trione (4)mentioning

confidence: 99%

Rhodium-Catalyzed C–H Activation of Indoles for the Construction of Spiroindole Scaffolds

Dai

Wang

et al. 2022

Synthesis

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Spiroindoles are key scaffolds in a large number of natural products, pharmaceuticals and agrochemicals. Selectively C–H activation has emerged as a powerful synthetic approach to streamline the synthesis of substituted spiroindoles. To date, various 2- and 3 indolyl-tethered aza-spiro-centres have been successfully achieved via C−H activation. However, introduction of spiro-containing systems onto the benzenoid core of indole still remains challenging. Herein, we reported a method of Rh(III)-catalyzed selectively C7−H activation/cyclization of indole with maleimide to afford novel spiroindole derivatives, which incorporated both succinimide and spirocycle into indole unit. Gram-scale synthesis demonstrated the utility of this protocol, further modification via click chemistry offered the novel scaffold as a versatile spiro linker.

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Synthesis of α,ω-heterotelechelic PVP for bioconjugation, via a one-pot orthogonal end-group modification procedure

Abstract: A simple one pot orthogonal procedure for synthesizing α-aldehyde, ω-thiol heterotelechelic poly(N-vinylpyrrolidone) (PVP) is introduced.

Cited by 17 publications

References 40 publications

Telechelic polymers from reversible-deactivation radical polymerization for biomedical applications

Telechelic polymers from reversible-deactivation radical polymerization for biomedical applications

Synthesis of Well-Defined Pyrrolidone-Based Homopolymers and Stimulus-Responsive Diblock Copolymers via RAFT Aqueous Solution Polymerization of 2-(N-Acryloyloxy)ethylpyrrolidone

Rhodium-Catalyzed C–H Activation of Indoles for the Construction of Spiroindole Scaffolds

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