Thiol–ene “click” reactions and recent applications in polymer and materials synthesis: a first update

Abstract

This contribution serves as an update to a previous review (Polym. Chem. 2010, 1, 17–36) and highlights recent applications of thiol–ene ‘click’ chemistry as an efficient tool for both polymer/materials synthesis as well as modification.

Amino acid-incorporated polymer network by thiol-ene polymerization

“…We also reported a polymer network by the reaction of 4,4"-bismaleimidodiphenylmethane with L-lysine [36]. Recently, radical-mediated thiol-ene 'click' reactions have attracted increasing attention as a method for the production of crosslinked polymer networks with various frameworks and functional groups [37][38][39][40]. The radical thiol-ene reaction can be initiated by a variety of techniques including under traditional thermal conditions with common azo species such as 2,2"-azobis(isobutyronitrile) (AIBN) or via photochemical methods, with or without added photoinitiator.…”

Recent Advances in Photo-Induced Free-Radical Polymerization

“…In particular, thiol-ene photopolymers have gained increased attention in the design of functional materials for tissue engineering, nano-imprinting, shape memory or optical and microfluidic devices. 13,14 The propagation mechanism of the thiol-ene photopolymerization is an alternation of addition and chain transfer reactions. 15 The most important factor governing the overall kinetics of thiol-ene polymerization is the ratio of the propagation rate constant (kp) to the chain-transfer rate constant, therefore, the reaction kinetics strongly depends on monomer structure.…”

Pursuing Chemical Efficiency by Using Supported Organocatalysts for Asymmetric Reactions under Aqueous Conditions

“…For instance, Hayashi incorporated an hexanoyloxy group at the 4-position of 4-hydroxy-L-proline, allowing its use in a water/oil emulsion [52] This position of the 4-hydroxy-Lproline has been used to support this molecule to several polymers following different synthetic strategies. For instance, this catalyst has been incorporated to a polystyrene Merrifield resin through a 1,3-dipolar cycloaddition reaction with the corresponding O-propargyl hydroxyproline derivative [53,55]. When 10 mol% of resin 5 ( Figure 1) was used in the aldol reaction between acyclic and cyclic alkyl ketones (3, 5 equiv.)…”