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On the structure-control relationship of amide-functionalized SG1-based alkoxyamines for nitroxide-mediated polymerization and conjugation

Abstract : The functionalization of alkoxyamines prior to nitroxide-mediated polymerization (NMP) induces important structural variations when compared to the parent molecules. This may have important consequences on the design of functionalized materials by pre-functionalization. In this context, a wide range of amide-functionalized alkoxyamines (a functionality often obtained after conjugation from COOH- and N-succinimidyl-containing alkoxyamines) based on the nitroxide SG1 (N-tert-butyl-N-(1-diethyl phosphono-2,2-dimethylpropyl) nitroxide) have been synthesized and their dissociation rate constants (k(d)) have been determined. To rationalize their reactivity, a multi-parameter procedure was applied and enabled to discriminate disubstituted amide-functionalized alkoxyamines from monosubstituted ones. Monosubstituted alkoxyamines exhibited lower k(d) than their disubstituted counterparts (E-a increase of similar to 7-10 kJ mol(-1)) because of the occurrence of intramolecular hydrogen bonding (IHB) between the alkyl and the nitroxide fragments. NMP of styrene, n-butyl acrylate and methyl methacrylate with a small amount of acrylonitrile was then successfully performed from two representative secondary SG1-based alkoxyamines employed for conjugation: namely AMA (COOH-containing) and AMA-NHS (N-succinimidyl derivative), and compared to polymerizations initiated with AMA-Gem, an AMA-based alkoxyamine pre-functionalized with the anticancer drug Gemcitabine (Gem) and subjected to IHB. Although AMA-NHS showed the best results due to its lower Ea, the strong polarity of the Gem moiety that counter-balanced the detrimental effect of IHB over its kd still allowed for a reasonable control.
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https://hal-amu.archives-ouvertes.fr/hal-01415150
Contributor : Didier Siri <>
Submitted on : Monday, December 12, 2016 - 6:49:02 PM
Last modification on : Monday, October 12, 2020 - 11:30:05 AM

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Elise Guegain, Vianney Delplace, Thomas Trimaille, Didier Gigmes, Didier Siri, et al.. On the structure-control relationship of amide-functionalized SG1-based alkoxyamines for nitroxide-mediated polymerization and conjugation. Polymer Chemistry, Royal Society of Chemistry - RSC, 2015, 6 (31), pp.5693--5704. ⟨10.1039/c5py00283d⟩. ⟨hal-01415150⟩

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