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. 2023 Apr 26;15(9):2052.
doi: 10.3390/polym15092052.

A Biodegradable, Polymer-Supported Oxygen Atom Transfer Reagent

Erin E Ramey  1 , Elizabeth L Whitman  2 , Cole E Buller  1 , James R Tucker  2 , Charles S Jolly  2 , Kjersti G Oberle  1 , Austin J Becksvoort  1 , Mark Turlington  2 , Christopher R Turlington  1
Affiliations

A Biodegradable, Polymer-Supported Oxygen Atom Transfer Reagent

Erin E Ramey et al. Polymers (Basel). .

Abstract

Biodegradable polymers are desirable to mitigate the environmental impact of plastic waste in the environment. Over the past several decades, the development of organocatalytic ring-opening polymerization (OROP) has made the synthesis of many new types of biodegradable polymers possible. In this research article, the first example of an oxygen atom transfer reagent pendant on a biodegradable polymer backbone is reported. The monomers for the polycarbonate backbone are sourced from the biodegradable 2,2-bis(hydroxymethyl) propionic acid molecule, and an iodoaryl group is installed pendant to the cyclic monomer for post-polymerization modification into an iodosylaryl oxygen atom transfer reagent. The key I-O bond is characterized by XPS spectroscopy, and a test reaction to triphenylphosphine demonstrates the ability of the polymer to engage in an oxygen atom transfer reaction with a substrate.

Keywords: biodegradable polymers; organocatalytic ring-opening polymerization; oxygen atom transfer.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Two polymer-supported, oxygen atom transfer reagents that are not biodegradable.
Figure 2
Figure 2
The biodegradable bis-MPA molecule for biodegradable monomer and polymer synthesis.
Figure 3
Figure 3
Synthesis of ArI-TMC, a cyclic trimethylene carbonate monomer with a pendant iodoaryl group.
Figure 4
Figure 4
Homopolymerization of the ArI-TMC monomer and the polymer peak in the GPC-UC spectrum (inset).
Figure 5
Figure 5
Disproportionation reaction of iodosylarenes. The ArIO2 product is not a strong oxygen atom transfer reagent.
Figure 6
Figure 6
Copolymerization of Bn-TMC monomer and ArI-TMC monomer.
Figure 7
Figure 7
Reaction rates for the copolymerization of 50% Bn-TMC monomer and 50% ArI-TMC monomer.
Figure 8
Figure 8
Oxidation of the iodoaryl groups to iodosylaryl groups in the copolymer. (a) Overall oxidation of the copolymer. (b) Reaction sequence occurring at the iodoaryl groups.
Figure 9
Figure 9
Expansion of the XPS region showing the resonance for iodine in the iodosylaryl copolymer.
Figure 10
Figure 10
Reaction testing the oxidizing capability of the iodosylaryl copolymer.
See this image and copyright information in PMC

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