Pentafluorobenzene end-group as a versatile handle for para fluoro “click” functionalization of polythiophenes

Boufflet, Pierre; Casey, Abby; Xia, Yiren; Stavrinou, Paul N.; Heeney, Martin

doi:10.1039/c6sc04427a

Cited by 40 publications

(36 citation statements)

References 91 publications

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“…19 Multifunctional PFB-functional building blocks have been condensed for the preparation of metal-containing linear polymers, 20 hyperbranched polymers, 21 and precision networks. 22 PFB-functionalised end groups were exploited for the functionalization of polythiophenes 23 and the synthesis of multi-arm copolymers. 24 With regards to postpolymerization functionalization of side groups, however, the literature is, with very few exeptions, 21,[25][26][27][28] pentafluorostyrene-based (co)polymers with amines, 29 phosphite, 30 and thiols [31][32][33] (including in water 34 and on surfaces).…”

Section: Introductionmentioning

confidence: 99%

Para-Fluoro Postpolymerization Chemistry of Poly(pentafluorobenzyl methacrylate): Modification with Amines, Thiols, and Carbonylthiolates

et al. 2017

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A methacrylic polymer undergoing highly efficient para-fluoro substitution reactions\ud is presented. A series of well-defined poly(2,3,4,5,6-pentafluorobenzyl methacrylate) (pPFBMA)\ud homopolymers with degrees of polymerization from 28 to 132 and Ð ≤ 1.29 was prepared by the\ud RAFT process. pPFBMA samples were atactic (with triad tacticity apparent in 1H and 19F NMR\ud spectra) and soluble in most organic solvents. pPFBMA reacted quantitatively through parafluoro\ud substitution with a range of thiols (typically 1.1 equiv thiol, base, RT, < 1h) in the absence\ud of any observed side reactions. Para-fluoro substitution with different (thio)carbonylthio\ud reagents was possible and allowed for subsequent one-pot cleavage of dithioester pendent groups\ud with concurrent thia-Michael side group modification. Reactions with aliphatic amines (typically\ud 2.5 equiv amine, 50–60 °C, overnight) resulted in complete substitution of the para-fluorides\ud without any observed ester cleavage reactions. However, for primary amines, H2NR, double\ud substitution reactions yielding tertiary (–C6F4)2NR amine bridges were observed, which were\ud absent with secondary amine reagents. No reactions were found for attempted modifications of\ud pPFBMA with bromide, iodide, methanethiosulfonate, or thiourea, indicating a highly selective\ud reactivity toward nucleophiles. The versatility of this reactive platform is demonstrated through\ud the synthesis of a pH-responsive polymer and novel thermoresponsive polymers: an\ud oligo(ethylene glycol)-functional species with an LCST in water and two zwitterionic polymers\ud with UCSTs in water and aqueous salt solution (NaCl concentration up to 178 mM)

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Section: Introductionmentioning

confidence: 99%

Para-Fluoro Postpolymerization Chemistry of Poly(pentafluorobenzyl methacrylate): Modification with Amines, Thiols, and Carbonylthiolates

et al. 2017

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“…Post-polymerization α-functionalization of PTP with an α-trimethoxy functional thiol. 54 Also, the solvolysis and condensation reactions of PEG diol with tetraethoxy-or tetramethoxy-silane (H + catalyst, MeOH or THF, 50 °C, 30 min) provided the corresponding trialkoxysilyl end-capped PEG oligomers, ultimately affording gels, as reported by Vincens and coworkers. 63 Reaction of the hydroxyl end groups of three PEG moieties bound to a molybdenum center with Cl(CH 2 ) 3 Si(OEt) 3 afforded the corresponding tris[(triethoxy)silyl] functionalized organometallic complex.…”

Section: Omementioning

confidence: 66%

Advances in the synthesis of silyl-modified polymers (SMPs)

Guillaume

2018

Polym. Chem.

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“…The introduction of “click” handles during a direct functionalization step is often used to enable the divergent modification of a parent material leading to a library of materials with the same backbone structure. For example, Heeney and coworkers recently reported that a pentafluorophenyl group can be incorporated as a versatile “click” handle, enabling a range of nucleophilic aromatic substituions . Specifically, this method achieved up to 70% monofunctionalization, and enabled the incorporation of sensitive moieties, including biotin and a trialkylsiloxane unit (Fig.…”

Section: Discussionmentioning

confidence: 99%

Established and emerging strategies for polymer chain‐end modification

Lunn

Discekici

Alaniz

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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The development of "controlled" and "living" polymerization processes with high end-group fidelity has enabled an unprecedented range of polymeric materials with specific chainend functionality to be prepared. This highlight provides an overview of available strategies and evaluation of recent approaches for the chain-end functionalization of polymers prepared through controlled chain-growth polymerizations. As a tribute to Professor Robert B. Grubbs on the occasion of his 75th birthday, we also take this opportunity to highlight methods for the chain-end modification of polymers prepared by ring-opening metathesis polymerization within the broader context of functional group tolerant, living polymerizations. Finally, we focus attention toward new directions in polymer chain-end modifications, describing existing gaps in current strategies, and detailing recently reported protocols that show significant improvements over traditional methods.

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Pentafluorobenzene end-group as a versatile handle for para fluoro “click” functionalization of polythiophenes

Abstract: Inclusion of a perfluorophenyl endgroup enables the ready functionalization of water soluble polythiophenes under mild conditions.

Cited by 40 publications

References 91 publications

Para-Fluoro Postpolymerization Chemistry of Poly(pentafluorobenzyl methacrylate): Modification with Amines, Thiols, and Carbonylthiolates

Para-Fluoro Postpolymerization Chemistry of Poly(pentafluorobenzyl methacrylate): Modification with Amines, Thiols, and Carbonylthiolates

Advances in the synthesis of silyl-modified polymers (SMPs)

Established and emerging strategies for polymer chain‐end modification

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