Allyl group-containing polyvinylphosphonates as a flexible platform for the selective introduction of functional groups via polymer-analogous transformations

Polyvinylphosphonates are highly promising candidates for (bio)medical applications as they exhibit a tunable lower critical solution temperature, high biocompatibility of homo- and copolymers, and a broad foundation for post-synthetic modifications. In this work we explored polymer-analogous transf...

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Bibliographic Details
Published in:RSC advances 2021-11, Vol.11 (61), p.38555-38564
Main Authors: Halama, Kerstin, Schaffer, Andreas, Rieger, Bernhard
Format: Article
Language:English
Subjects:
Alkynes
Biocompatibility
Bromination
Chemical analysis
Chemical synthesis
Chemistry
Conjugates
Copolymers
Copper converters
Coupling (molecular)
Epoxidation
Functional groups
Hydrazones
Liquid chromatography
NMR
Nuclear magnetic resonance
Polymers
Sodium azides
Substrates
Transformations
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Summary:Polyvinylphosphonates are highly promising candidates for (bio)medical applications as they exhibit a tunable lower critical solution temperature, high biocompatibility of homo- and copolymers, and a broad foundation for post-synthetic modifications. In this work we explored polymer-analogous transformations with statistical polyvinylphosphonates comprising diethyl vinylphosphonate (DEVP) and diallyl vinylphosphonate (DAlVP). The C[double bond, length as m-dash]C double bonds were used as a starting point for a cascade of organic transformations. Initially, the reactive moieties were successfully introduced bromination, epoxidations with and CPBA, or thiol-ene click chemistry with methyl thioglycolate (6). The obtained substrates were then employed in a variety of consecutive reactions depending on the introduced functional motif: (1) the brominated substrates were converted with sodium azide to enable the copper-mediated alkyne-azide coupling with phenylacetylene (1). (2) The epoxides were reacted with sodium azide for an alkyne-azide click coupling with 1 as well as small nucleophilic compounds (phenol (2), benzylamine (3), and 4-amino-2,1,3-benzothiadiazol (4)). Afterwards the non-converted allyl groups were reacted with thiochloesterol (5) to form complex polymer conjugates. (3) An acid-labile hydrazone-linked conjugate was formed in a two-step approach. The polymeric substrates were characterized by NMR, FTIR, and UV/Vis spectroscopy as well as elemental analysis and gel permeation chromatography to monitor the structural changes of the polymeric substrates and to prove the success of these modification approaches.
ISSN:2046-2069
2046-2069
DOI:10.1039/d1ra06452e