Inspired by the uniqueness and ubiquity of thioesters in nature, much attention has been paid to thioester functionalized materials, yielding applications ranging from responsive polymers to bioconjugates and (bio)degradable polymers.

A strategy for the synthesis of sequence-defined oligomers using a selective side-group insertion approach making use of thiophenol-catalyzed amidation reactions is herein reported. In this context, a new thiolactone-based, multistep, iterative protocol is designed, utilizing thioacrylates in combination with solid-phase synthesis for step-by-step growth, resulting in sequence-defined oligomers. Sequence definition and structure variation are introduced by substituting the thioacrylate side groups with a wide variety of amines. The step-by-step growth of the oligomers is followed by liquid chromatography-mass spectrometry and high-resolution mass spectroscopy to determine both conversion and purity.

A facile method for synthesizing thioacrylate monomers and their RAFT polymerization have been demonstrated for the first time.

Nitroxide mediated polymers of thioacrylates can be transformed into poly(acrylamide)s.

Ethyl thioacrylate was polymerised via Cu-RDRP and subjected to amidation to obtain the first “all-acrylic” copolymer.