A Green Approach for the Synthesis and Thiol‐ene Modification of Alkene Functio1489lized Poly(2‐oxazoline)s

Abstract

The bulk polymerization of 2-(dec-9-enyl)-2-oxazoline (DecEnOx), a fatty acid-based monomer for the cationic ring-opening polymerization, is reported. Furthermore, under optimal conditions, namely microwave heating at 100 °C, the bulk copolymerization with 2-ethyl-2-oxazoline yielded well-defined copolymers. Due to its pendant alkene groups DecEnOx-based polymers possess the potential to be modified in efficient thiol-ene reactions. The functionalization with thiols, e.g., dodecanethiol and 2,3,4,6-tetra-O-acetyl-1-thio-β-D-glycopyranose in "green" solvents is demonstrated.

Design Strategies for Functionalized Poly(2-oxazoline)s and Derived Materials

“…Schubert, Hoogenboom and Kempe reported that, due to its double bonds in the side-chains, p n Dec = Ox can be crosslinked and as well be modified by thiol-ene reactions with thiols such as n-dodecanethiol or 2,3,4,6-tetra-O-acetyl-1-thio-glucopyranose (Scheme 15) [183]. Nuyken and colleagues prepared random copolymers of the composition p(SH)EtOx-stat-pEtOx from the CROP of (SBz)EtOx and EtOx and subsequent deprotection of the thiol function [184].…”

RGD-Functionalization of Poly(2-oxazoline)-Based Networks for Enhanced Adhesion to Cancer Cells

“…The UV-induced crosslinking of poly(2-oxazoline)-based copolymers with oligovalent thiols and the functionalization of decenyl side-chains of poly(2-oxazoline)s by thiol-ene reactions have been described in the literature [31][32][33]. In this study, the concept was transferred to the functionalization of ground gel particles in suspension by thiol-ene reactions, benefiting from the fact that they are insensitive to water [39].…”

“…The gels were subsequently tested for loadability with the fluorescent dye, fluorescein isothiocyanate (FITC) (Scheme 1). Inclusion of Dc = Ox with unsaturated side-chains in the copoly(2-oxazoline) chains enabled the surface functionalization of ground hydrogels by thiol-ene reactions [31][32][33]. Notably, due to in situ crosslinking with a bisfunctional monomer and subsequent functionalization by thiol-ene, the reactions enabled orthogonal syntheses.…”

Poly(2-oxazoline)s and click chemistry: A versatile toolbox toward multi-functional polymers

“…Hoogenboom, Schubert et al reported on a green approach for the synthesis of 2-decenyl-2-oxazoline (DecenOx) based on naturally derived undecenoic acid, in which traditionally used organic solvents such as dichloromethane and methanol were replaced by 2-methyltetrahydrofuran (mTHF), a solvent obtained from waste biomass. 62 As the (co)polymerization of DecenOx was performed in bulk and the subsequent UV-initiated thiol-ene click reaction proceeded in mTHF or methyl laurate, this represents a green alternative towards functional PAOx. Furthermore, the carbodiimide / N-hydroxysuccinimide system was applied for the synthesis of an azidofunctionalized 2-oxazoline monomer, using 6-azidohexanoic acid as starting material by Udet and coworkers.…”